Kinda Jouna VETTİ

MARMARA UNIVERSITY
I N S TIT UTE F O R G RAD UATE S T U D I E

S I N PU R EAN DAPPLI E D S C I E N C E S
SYNTHESIS, OPTIMIZATION, AND CHARACTERIZATION
OF METAL-ORGANIC FRAMEWORKS (MOF)
AS EFFICIENT ELECTROCATALYSTS FOR HYDROGEN PRODUCTION

FROM WATER
KİNDA JOUNA VETTİ
524521991
MASTER THESIS
Department of Chemical Engineering
Thesis Supervisor
Prof. Dr. Atıf KOCA
ISTANBUL, 2023
i
MARMARA UNIVERSITY
I N S TIT UT E F O R G RAD UATE S T U D I E

S I N PU R EAN DAPPLI E D S C I E N C E S
SYNTHESIS, OPTIMIZATION, AND CHARACTERIZATION
OF METAL-ORGANIC FRAMEWORKS (MOF)
AS EFFICIENT ELECTROCATALYSTS FOR HYDROGEN PRODUCTION

FROM WATER
KİNDA JOUNA VETTİ
524521991
MASTER THESIS
Department of Chemical Engineering
Thesis Supervisor
Prof. Dr. Atıf KOCA
ISTANBUL, 2023
ii
MARMARA ÜNİVERSİTESİ FEN BİLİMLERİ ENSTİTÜSÜ
Marmara Üniversitesi Fen Bilimleri Enstitüsü Yüksek Lisans Öğrencisi Kinda Jouna VETTİ’un
“Synthesis, Optimization, And Characterization of Metal-Organic Frameworks (MOF)As Efficient
Electrocatalysts for Hydrogen Production From Water” başlıklı tez çalışması, ……... tarihinde
savunulmuş ve jüri üyeleri tarafından başarılı bulunmuştur.
Jüri Üyeleri
Prof. Dr. Atıf KOCA (Danışman)

Marmara Üniversitesi .....................................................................(İMZA).................
Marmara Üniversitesi .....................................................................(İMZA).................
İstanbul Üniversitesi .......................................................................(İMZA).................
ONAY
Marmara Üniversitesi Fen Bilimleri Enstitüsü Yönetim Kurulu’nun ………. tarih ve sayılı kararı
ile Kinda Jouna VETTİ’un Kimya Mühendisliği Anabilim Dalı Kimya Mühendisliği Programında
Yüksek Lisans derecesi alması onanmıştır.
Fen Bilimleri Enstitüsü Müdürü
Prof. Dr. Bülent EKİCİ
iii
MARMARA UNIVERSITY INSTITUTE OF NATURAL SCIENCES
Kinda Jouna VETTİ, a Master of Science student at Marmara University Institute for
Graduate Studies in Pure and Applied Sciences defended her thesis entitled “Synthesis,
Optimization, And Characterization of Metal-Organic Frameworks (MOF) As Efficient
Electrocatalysts for Hydrogen Production from Water ”, on ……. and has been found to be
satisfactory by the jury members.
Jury Members
Prof. Dr. Atıf KOCA (Advisor)

Marmara University .........................................................................(SIGN) ...............
Marmara University ..........................................................................(SIGN) ...............
İstanbul University............................................................................(SIGN)...............
APPROVAL
Marmara University Institute for Graduate Studies in Pure and Applied Sciences Executive
Committee approves that Kinda Jouna VETTİ be granted the degree of Master of Science in
Department of Chemical Engineering, Chemical Engineering Program on …… (Resolution
no:................).
Director of the Institute
Prof. Dr. Bülent EKİCİ
iv
ACKNOWLEDGEMENT
I am deeply grateful to Prof. Dr. Atıf KOCA, my supervisor, whose unwavering

support and guidance were instrumental in completing this scientific work.
His consistent motivation and adept assistance helped me navigate through
every stage of this research endeavour.
I owe an immense debt of gratitude to my steadfast companion and best

friend, Hasan VETTI, whose unwavering emotional support and unshakable
faith in my abilities significantly enriched the quality of this dissertation. I
am indebted to my daughter, small angel Limar VETTI, whose enduring smile
has been a constant source of inspiration and purpose in my life.
To my cherished family members my father M. Khaldoun JOUNA, beloved

sisters, and dear brother whose unwavering love and unwavering support,
despite the distance, have been a constant source of strength throughout this
academic journey.
I carry the memory and inspiration of my late mother Dounia MOUSTO, whose
belief in my aspirations continues to guide and inspire me. I am certain her
presence is felt beside me, driving me to excel and make her proud."
January 2024 Kinda Jouna VET
i
TABLE OF CONTENTS
ACKNOWLEDGEMENT ..................................................................................................... i
ABSTRACT ..........................................................................................................................vi
SUMMARY (ÖZET) ........................................................................................................... viii
SYMBOLS ............................................................................................................................ x
ABBREVIATION .................................................................................................................xi
TABLE OF FIGURES: ........................................................................................................ xii
LIST OF TABLES............................................................................................................... xvi
1. INTRODUCTION ......................................................................................................... 1
1.1. Hydrogen Energy ...................................................................................................... 1
1.1.1. H2 Production ........................................................................................................ 1
1.1.2. H2 Storage ............................................................................................................. 2
1.1.2.1. Physical-Based H2 Storage ................................................................................ 2
1.1.2.2. Material-Based H2 Storage ................................................................................ 3
1.2. Technologies For Hydrogen Production .................................................................... 4
1.2.1. Hydrogen Production from Fossil Fuels ............................................................... 4
1.2.1.1. Fossil Hydrocarbon Reforming Technologies. .................................................. 4
1.2.1.1.1. Steam Reforming............................................................................................... 5
1.2.1.1.2. Partial Oxidation. .............................................................................................. 5
1.2.1.2. Fossil Hydrocarbon Pyrolysis ........................................................................... 6
1.2.1.2.1. Coal Gasification. .............................................................................................. 6
1.2.2. Hydrogen Production from Renewable Resources................................................ 7
1.2.2.1. Hydrogen Production from Water...................................................................... 7
1.2.2.1.1. Electrolysis ........................................................................................................ 7
1.2.2.1.2. Thermolysis ....................................................................................................... 8
1.2.2.1.3. Photo Electrolysis.............................................................................................. 8
1.2.2.1.4. Bio Photolysis. .................................................................................................. 8
1.2.2.2. Hydrogen Production from Biomass. ................................................................ 9
1.2.2.2.1. Biological Processes .......................................................................................... 9
1.3. Hydrogen Production from Water Electrolysis ......................................................... 9
1.3.1. Classification Of Water Electrolysis Technologies ............................................. 10
1.3.2. Electrochemical Reactions in Water Electrolysis ................................................ 12
1.3.3. Electrocatalyst Used in Electrolysis. ................................................................... 13
1.3.3.1. Homogeneous Electrocatalysts........................................................................ 14
ii
1.3.3.1.1. Enzymes .......................................................................................................... 15
1.3.3.2. Heterogeneous Electrocatalysts ....................................................................... 15
1.3.3.2.1. Bulk Materials ................................................................................................. 15
1.3.3.2.2. Nanomaterials.................................................................................................. 16
1.3.3.2.2.1. Nanoparticles ............................................................................................... 16
1.3.3.2.2.2. Carbon-Based Materials .............................................................................. 16
1.3.3.2.2.3. Framework Materials .................................................................................. 16
1.4. Metal−Organic Frameworks.................................................................................... 17
1.4.1. Introduction ......................................................................................................... 17
1.4.1.1. Chemistry ........................................................................................................ 18
1.4.2. MOFs Synthesis .................................................................................................. 19
1.4.2.1. Sonochemical Synthesis .................................................................................. 20
1.4.2.2. Conventional Solution Method ....................................................................... 20
1.4.2.3. Diffusion Synthesis Method ............................................................................ 20
1.4.2.4. Iono-Thermal Process ..................................................................................... 21
1.4.2.5. Microwave Synthesis ...................................................................................... 21
1.4.2.6. Electrochemical Synthesis............................................................................... 21
1.4.2.7. Solvothermal Synthesis Method...................................................................... 21
1.4.3. MOF Properties and Applications ....................................................................... 24
1.4.4. Applications of MOF Electrocatalysts In Overall Water Electrolysis ................. 32
1.4.4.1. MOF-Based Overall Water Splitting Electrocatalysts. .................................... 32
1.4.4.2. MOF-Derived Overall Water Splitting Electrocatalysts. ................................. 34
1.4.5. Applications Of MOF-Based/MOF-Derived Electrocatalysts For HER ............. 35
1.4.5.1. HER Main Mechanisms .................................................................................. 35
1.4.5.2. MOF-Based HER Electrocatalysts .................................................................. 37
1.4.5.2.1. Noble Metal-Based Electrocatalysts. .............................................................. 37
1.4.5.2.2. Transition Metal-Based Electrocatalysts. ........................................................ 40
1.4.5.2.3. Examples Of the Most Active HER- MOFs Electrocatalysts .......................... 45
2. Experimental Method .................................................................................................. 50
2.1. Materials. ................................................................................................................. 50
2.2. Synthesising Different Types of Transition Metals-Based MOF As HER
Electrocatalyst ..................................................................................................................... 50
2.2.1. Synthesis Of Mono-MOF With Solvothermal Preparation Methods .................. 50
2.2.1.1. Calcination Process for Co-Based MOF ......................................................... 51
2.2.1.2. Calcination And Metal Loading Process for Co-Based MOF ......................... 52
iii
2.2.2. Synthesis Of Bimetallic -MOF With Different Preparation Methods ................. 52
2.2.2.1. Synthesis Of Co.Fe. MOFs With Preparation Method(A) .............................. 52
2.2.2.1.1. Calcination And Metal Loading Process for Bimetallic Co.Fe. MOFs ........... 53
2.2.2.2. Synthesis Of Co.Fe. MOFs With Preparation Method(B) ............................... 53
2.2.2.2.1. Calcination And Metal Loading Process for Bimetallic Co.Fe. MOFs (B) ..... 54
2.3. Preparation of MOFs Ink Composite ...................................................................... 54
2.4. Catalyst Characterization Techniques: .................................................................... 55
2.4.1. FTIR Spectroscopic Studies ................................................................................ 55
2.4.2. XRD Measurements ............................................................................................ 55
2.5. Electrochemical Measurements ............................................................................... 55
3. RESULTS AND DISCUSSIONS: ............................................................................... 57
3.1. Synthesis Of Monometallic -MOF with Different Preparation Methods ................ 57
3.1.1. Synthesized Co-MOF Electrocatalyst Type with Solvothermal Methods ........... 57
3.1.1.1. Structural Characterization of Co.MOF Electrocatalyst: ................................ 57
3.1.1.1.1. Fourier Transform Infrared (FT-IR) Of Co.MOF Electrocatalyst: .................. 57
3.1.1.1.2. X-Ray Diffraction (XRD) Of Co.MOF Electrocatalyst: ................................. 59
3.1.1.2. Electrochemical Measurements ....................................................................... 60
3.1.1.2.1. Linear Sweep Voltammetry Analysis for Co.MOF Electrocatalyst Type: ....... 60
3.1.1.2.2. Tafel Slope Analysis for Co.MOF Electrocatalyst Type: ................................ 62
3.1.1.2.3. EIS-Electrochemical Impedance Spectroscopy for Co.MOF Electrocatalyst
Type: 63
3.1.1.2.4. HER Stability for Co.MOF Electrocatalyst Type: ........................................... 66
3.1.2. Cobalt Calcinated MOF, Cobalt Calcinated and Loaded with Iron and Cobalt. . 67
3.1.2.1. Linear Sweep Voltammetry Analysis for Co.C.MOF and Co.C.MOF/Fe.Co
Electrocatalyst Type: ........................................................................................................... 67
3.1.3. Synthesized Fe-MOF Electrocatalyst with Solvothermal Method ...................... 69
3.1.3.1. Structural Characterization of Fe.MOF Electrocatalyst: ................................. 69
3.1.3.1.1. Fourier Transform Infrared (FT-IR) Of Fe.MOF Electrocatalyst: ................... 69
3.1.3.1.2. X-Ray Diffraction (XRD) Of Fe.MOF Electrocatalyst: .................................. 70
3.1.3.2. Electrochemical Measurements:...................................................................... 71
3.1.3.2.1. Linear Sweep Voltammetry Analysis for Fe-MOF Electrocatalyst Type: ....... 71
3.1.3.2.2. Tafel Slope Analysis for Fe-MOF Electrocatalyst Type: ................................. 74
3.1.3.2.3. EIS-Electrochemical impedance spectroscopy for Fe-MOF electrocatalyst
type: 75
3.1.3.2.4. HER Stability for Fe-MOF Electrocatalyst Type: ........................................... 78
iv
3.2. Synthesis Of Bimetallic -MOF With Different Preparation Methods ..................... 79
3.2.1. Synthesized Co.Fe. MOF Electrocatalyst, Calcination and Metal Loading (A): 79
3.2.1.1. Structural Characterization of Co.Fe.C.MOF/Co. Fe(A) Electrocatalyst: ...... 79
3..2.1.1.1. Fourier Transform Infrared (FT-IR) of Co.Fe.C.MOF/Co. Fe(A) Electrocatalyst:
............................................................................................................................................. 79
3.2.1.2. Electrochemical Measurements ....................................................................... 80
3.2.1.2.1. Linear Sweep Voltammetry Analysis for Co. Fe.MOF And Co. Fe.C.MOF/Fe.
Co(A) Electrocatalyst Type. ................................................................................................ 80
3.2.1.2.2. Tafel Slope Analysis for Co. Fe.C.MOF/Fe. Co(A) Electrocatalyst Type....... 83
3.2.1.2.3. EIS-Electrochemical Impedance Spectroscopy Co. Fe.C.MOF/Fe. Co(A)
Electrocatalyst Type. ........................................................................................................... 84
3.2.1.2.4. HER Stability Co. Fe.C.MOF/Fe. Co(A) Electrocatalyst Type....................... 87
3.2.2. Synthesized Co.Fe. MOF Electrocatalyst, Calcination and Metal Loading (B): 87
3.2.2.1. Linear Sweep Voltammetry Analysis for Co. Fe.MOF And Co.Fe.C.MOF/Fe.
Co(B) Electrocatalyst Type: ................................................................................................ 87
3.3. Comparison Of Electrochemical Measurements for All MOFs Synthesized
Electrocatalyst Types. .......................................................................................................... 89
3.3.1. Comparisons Of Linear Sweep Voltammetry Analysis and Tafel Slope ............. 89
3.3.2. EIS-Electrochemical Impedance Spectroscopy Analysis .................................... 92
4. CONCLUSION ........................................................................................................... 94
REFERENCES .................................................................................................................... 96
AUTOBIOGRAPHY ........................................................................................................ 115
v
ABSTRACT
In the current time with increasing the global warming issue that is caused mainly by
increasing carbon dioxide level and other toxic gases because of using fossil fuel as a
main source of energy. consequently, it became too significant to spot the light on new
research area that relies on producing energy from renewables and sustainable sources.
Hydrogen production by utilizing water electrolysis technology is a promising technique
which represents clean energy source as well high energy-efficient fuel on the earth.
however, the major obstacle that hamper utilizing this incredible technology is finding
alternative electrocatalysts which are highly efficient, inexpensive, and earth-abundant
since Nobel metal-based catalysts are the most efficient electrocatalyst to drive the
cathodic and anodic reactions, but their high cost and scarcity limit water electrolysis.
In this research area Transition metal-based metal-organic framework (MOFs), have been
introduced as a promising electrocatalysts for developing hydrogen evolution reaction in
the electrochemical cell, due to their unique features starting from their ultrahigh porosity,
enormous internal surface area, extraordinary degree of variability, and their ability to
host external guest. Particularly, different types of these nanomaterials have been
synthesized including cobalt-based MOF, and iron-based MOF as monometallic MOFs
by using solvothermal method. then Co. Fe.MOF have been synthesized as a bimetallic
MOF with stirring and heating method, additionally calcination process and loading their
structure with metal ions have been conducted at the lab area by using CVD devise.
Optimization the effect of different parameters on the electrocatalytic efficiency such as
the solvent type, heating temperature and duration, and the ratio between metal and ligand
have been covered in this thesis plan.
FTIR Structural characterization technique of the as prepared electrocatalysts has been

performed and revealed on the structural vibration changing due to MOFs formations,
additionally XRD have been conducted and confirmed MOFs crystal formation through
sharp and intense diffraction peaks.
Remarkably, the vital evidences that prove the high HER catalytic activity have been
provided through the practical measurements that were done through lab experiments
appropriately with incredible achievement by utilizing Co.MOF to lower the HER
vi
overpotential to η10= 50mv to achieve a current density of 10 mA/cm2 and obtained
Tafel slope value 38.57 𝒎𝑽. 𝒅𝒆𝒄−𝟏 that indicate to high kinetic reaction provided by new
catalyst and resistance of charge transfer 𝑅𝐶𝑇 (Ω) to be 17.59ohm that approaches
commercial Pt/C catalyst which has about 42 mV of overpotential with Tafel slope about
34.32 𝒎𝑽. 𝒅𝒆𝒄−𝟏 .and resistance of charge transfer 𝑅𝐶𝑇 (Ω) about 2.569ohm furthermore
Fe.MOF also achieved another incredible overpotential reduction with η10= 46 mv and
Tafel value 46.71 𝒎𝑽. 𝒅𝒆𝒄−𝟏 resistance of charge transfer 𝑅𝐶𝑇 (Ω) to be 3.366 ohm. Add
to these research accomplishments another case study of bimetallic-MOF which is
Co.Fe.C.MOF/Co. Fe(A) with η10= 57 mv and Tafel slope about 37.01 𝒎𝑽. 𝒅𝒆𝒄−𝟏 .
resistance of charge transfer 𝑅𝐶𝑇 (Ω) to be 18. 25ohm.Consequently, the synthesized
MOFs have a great effect to enhance HER performance of the water electrolysis to
produce hydrogen efficiently, displaying high intrinsic activity compared to noble metals
(Pt). finally, MOFs catalysts showed a great stability after running LSV polarization curve
for 100 cycles.
The significance of this scientific work will be represented in successfully synthesizing

transition metal-based MOF as a highly efficient electrocatalyst with two distinctive case
study the first one shows the success in finding monometallic MOF catalysts with similar
performance to the Pt catalyst without any additional chemical process( remarkable
success through the preparation method its self), and the second case shows the
importance of the calcination process parameters to enhance the catalytic activity
(Co.Fe.C.MOF/Co. Fe(A))) (represent noticeable success in optimizing well the
calcination process with effective parameters).
This research study represents one of the most successful studies that were done and
mange to report lowest achieved overpotential at all since we manage to break off the
limitation for finding available and inexpensive catalysts that are competitive with
platinum catalysts that represent the major obstacles (being expensive and rare) that
hamper the development of more and more sophisticated hydrogen production systems.
vii
SUMMARY (ÖZET)
This research area mainly concentrated on developing hydrogen production system by

water electrolysis technology through finding and developing metal organic frame work
as a new types of electrocatalysts that relay on transition metal such as cobalt, nickel and
iron that have empty d orbitals, which can provide empty orbitals to behave as
electrophiles or provide lone pairs of electrons, because of that contributing to optimizing
the 3d electronic configuration, forming uniform active sites, and improving conductivity
(1). Furthermore, these metals will take place as part of MOF incredible structure with
high porosity and extraordinary surface area, and their capability to host within their
structure an external atom that can enhance the synergistic effects of the catalyst structure,
thereby promoting the improvements of the catalytic performance of the material.
Synthesizing different types of these nanoparticles such as Co.MOF, Fe.MOF as a

monometallic electrocatalysts, then Co. Fe.MOF as a bimetallic one was the fundamental
step, then manipulate their structures by preforming additional process to enhance their
catalytic activities, add to that changing the preparation methods, and optimizing the
effects of different parameters on the synthesizing process its self, then on the calcination
process again by changing the temperature and using different devices to see the
differences.
Cobalt based MOF and iron-based MOF samples were prepared by solvothermal methods
with using the autoclave as an efficient tool to ensure the reaction was done at high
temperature (180𝑐 𝑜 ) and pressure, for 24h with adding (Cobalt (II) nitrate hexahydrate/
iron (III) nitrate monohydrate) as metals salt and (benzimidazole) as an organic linker
with using more than one kind of solvent such as methanol, water and dimethyl
formamide (DMF). Calcination and loading with metal ions also took place as a next step
after harvesting the catalyst powder to see the effect of this process and its parameters on
the catalytic behavior.
As this research plan was processed navigating to prepare Co. Fe.MOF as a bimetallic
catalyst also was done as a developing step to increase the number of the active sites and
diversify MOFs structure, with new attempting to manipulate this diverse structure with
calcination and metal ions loading process with changing the parameters of the process
viii
again. With considering changing of the methods for synthesizing the bimetallic ones to
be with heating and stirring for one hour, with keeping the same types of solvents for case
(Co. Fe.MOF (A)) with different calcination process parameters and more develop CVD
device. and changing the solvent types to be one type DMF for (Co. Fe.MOF (B)) case
study.
Structural characterization of the as prepared electrocatalysts have been performed by

fundamental characterization techniques such as FTIR and XRD that are crucial to
understanding crystalline materials. particularly, these techniques were done for the best
three active electrocatalysts cases (Co.MOF, Fe.MOF, and (Co.Fe.C.MOF/Co. Fe(A)).
Fourier transform infrared spectroscopy (FTIR), has been used to determine the molecular
structure and functional groups providing information on the functional groups present in
the organic ligands, The crystallite of the as synthesized samples was identified using X-
ray diffraction peaks. The results of preforming FTIR and XRD confirmed that the crystal
structure of MOFs samples was formed appropriately through investigating the changing
in the structural vibrations of the BIM linker functional groups, then interpret the XRD
diffraction peaks that were a good indicator about the crystallites of prepared MOFs.
The HER electrocatalytic reaction performance of different MOFs sample has been
assessed by electrochemical analytical tools. More precisely, these utilized powerful
measurements that include LSV (linear sweep voltammetry) to provide valuable
information about the electrochemical reaction, and enable us to see the lowering value
of the overpotential, EIS (electrochemical impedance spectroscopy) have been carried
out to study the catalyst’s conductivity and the mass transfer between the electrolyte and
electrode, and the important parameters were extracted from fitting model of the Nyquist
plot and were interpreted well. Tafel slope that provide an idea about the electrochemical
reaction kinetics and the slope values were recorded and were a vital sign about the highly
kinetics reactions. Finally, the stability measurements by running LSV polarization curve
for 100 cycles to check the catalyst stability.
ix
SYMBOLS
𝑬(𝑹𝑯𝑬) : Obtained Potential of The Reversible Hydrogen Electrode
𝑬𝑨𝒈/𝑪𝒍 : The Obtained Values of Working Potential
𝜼 𝟏𝟎 : Overpotential At 10 Current Densities
𝒋 : Current Density.
b : Tafel Slop
𝜶 : Constant
𝑪𝒄 : Coating Capacity
𝑪𝒅𝒍 : Double Layer Capacitance
Ag/AgCl: Silver/Silver Chloride Electrode
𝑹𝒄𝒕 : Charge Transfer Resistance (Ohm)
𝑹𝒔 : Solution Resistance (Ohm)
𝑽𝒂𝒑𝒑 : Applied External Potential (V)
x
ABBREVIATION
MOF : Metal Organic Frame Work
Co.MOF : Cobalt Based Metal Organic Frame Work
Fe.MOF : Iron Based Metal Organic Frame Work
Co.C.MOF : Cobalt Calcinated Based Metal Organic Frame Work

: Cobalt Calcinated Based Metal Organic Frame Work
Co.C.MOF/Fe. Co
Loaded with Iron and Cobalt.
Co. Fe.MOF : Cobalt And Iron Based Metal Organic Frame Work.
Co.Fe.C.MOF/Fe. : Cobalt And Iron Calcinated Based Metal Organic
Co Loaded with Iron and Cobalt.
CVD : Chemical Vapor Deposition
DMF : Dimethylformamide
BIM : Benzimidazole
EIS : Electrochemical Impedance Spectroscopy
LSV : Linear Sweep Voltammetry
HER : Hydrogen Evolution Half Reaction
GCE : Glassy Carbon Electrode
TEM : Transmission Electron Microscopy
SEM : Scanning Electron Microscopy
XPS : X-Ray Photoelectron Spectroscopy
XRD : X-Ray Diffraction
FT-IR : Fourier Transform Infrared
RS : Raman Spectroscopy
EtOH : Ethanol
TEA : Triethylamine
TOF : Turn Over Frequency
xi
TABLE OF FIGURES:
FIGURE 1 THE SPECTRUM OF H2 PRODUCTION PROCESSES ................................................ 2

FIGURE 2 H2 STORAGE METHODS ...................................................................................... 4
FIGURE 3 SCHEMATIC ILLUSTRATION OF A. ALKALINE ELECTROLYSIS, B. SOLID OXIDE
ELECTROLYSIS, C. PROTON EXCHANGE MEMBRANE ELECTROLYSIS ........................... 10
FIGURE 4 A FLOW CHART CLASSIFYING THE TYPES OF MATERIALS THAT CAN SERVE AS
ELECTROCATALYSTS, INCLUDING HOMOGENEOUS AND HETEROGENEOUS
ELECTROCATALYSTS. ................................................................................................ 14
FIGURE 5 ILLUSTRATION OF MOF’S BUILDING BLOCKS AND RESULTING POROUS,

CRYSTALLINE STRUCTURE. ....................................................................................... 18
FIGURE 6 MOFS RESULTING FROM DIFFERENT METAL NODES AND BRIDGING

LIGANDS.(78). .......................................................................................................... 18
FIGURE 7 DIFFERENT METHODS OF MOF SYNTHESIS, (A) SONO-CHEMICAL SYNTHESIS

METHOD, (B) CONVENTIONAL SOLUTION METHOD, (C) DIFFUSION SYNTHESIS
METHOD, (D) IONO-THERMAL PROCESS METHOD, (E) MICROWAVE SYNTHESIS
METHOD, (F) ELECTROCHEMICAL SYNTHESIS METHOD, AND (G) SOLVOTHERMAL
SYNTHESIS METHOD. ................................................................................................ 19

FIGURE 8 SCHEMATIC ILLUSTRATION SHOWING STABLE MOFS COMPOSED OF METAL
CLUSTERS. (BLUE OR ORANGE BALLS), ORGANIC LINKERS (GREY LINES) AND
DANGLING FUNCTIONAL GROUPS (GREEN OR PINK SEGMENTS) FOR DIVERSE
APPLICATIONS. (98) .................................................................................................. 24
FIGURE 9 (A) THE NH2-MIL-88B(FE2NI)-MOF / NF SYNTHETIC PROCESS SCHEMATIC

DIAGRAM. USING NFN-MOF/NF AS THE ANODE AND CATHODE IN A WHOLE CELL
SETUP: (B) WHEN OPERATING AT A HIGH CURRENT DENSITY AND (C) FOLLOWING SUCH
OPERATION. (D) THE TOTAL WATER ELECTROLYSIS PERFORMANCE LSV CURVE, AND
(E) THE ACCOMPANYING TAFEL PLOTS.(133) COPYRIGHT 2018, WILEY-VCH.

SCHEMATIC DIAGRAM OF NH2-MIL-88B(FE2NI)-MOF /NF SYNTHETIC PROCESS. . 33
FIGURE 10 (A) SCHEMATIC DIAGRAM OF THE PREPARATION ROUTE OF CO-NC/CF. THE
LSV CURVES DIAGRAM OF (B) HER AND (D) OER IN 1 M KOH. (C, E) FREE ENERGY
DIAGRAM. (135) COPYRIGHT 2020, ROYAL SOCIETY OF CHEMISTRY. ..................... 35
FIGURE 11 CATALYTIC PROCESS MECHANISM DIAGRAM ON THE CATALYST SURFACE UNDER
ACIDIC (A) AND ALKALINE (B) CONDITIONS. (144) ROYAL SOCIETY OF CHEMISTRY
xii
COPYRIGHT 2021. (C) THE CONNECTION BETWEEN ACTIVITY AND H FREE BINDING
ENERGY. THE CURVE IS DERIVED FROM THE MICROKINETIC THEORY, AND THE CIRCLES
REPRESENT THE EXPERIMENTAL RESULTS. THE SCALING RELATIONSHIP BETWEEN THE
ACTIVATION BARRIER AND H FREE BINDING ENERGY IN THE VOLMER AND TAFEL
STAGES (D) AND (E).(142) COPYRIGHT 2018, WILEY-VCH. .................................... 37
FIGURE 12 A. (A) FT-EXAFS PROFILES OF NI-MOF@PT. (B) STRUCTURE DIAGRAM AT

NI-MOF@PT. (C) THE CURVE FOR LINEAR SWEEP VOLTAMMETRY (LSV).(145)
COPYRIGHT 2019, AMERICAN CHEMICAL SOCIETY. B. (A) RU@NI-MOF STRUCTURE
DIAGRAM. THE RU@NI-MOF DIAGRAMS OF (B) H2O ADSORPTION ENERGY AND (C)
ΔGH* DIAGRAM. (146) COPYRIGHT 2021, WILEY-VCH. C. THE ELECTRICAL

STRUCTURE OF THE METAL CORE IS CONTROLLED BY INDIVIDUAL NOBLE METAL
ATOMS. (A) DIAGRAM SHOWING THE NIRU0.13-BDC ELECTROCATALYST
PREPARATION PROCEDURE. (B) NIRU0.13-BDC'S LSV CURVE IN 1 M PBS. (C) THE
CHARGE DENSITY DIFFERENCE DIAGRAM. (D) NI-BDC AND NIRU0.13-BDC DOS
CALCULATIONS. (E) NIRU0.13-BDC'S COMPUTED FREE ENERGY DIAGRAM OF THE
HER (147) COPYRIGHT 2021, NATURE PUBLISHING GROUP. ................................... 40

FIGURE 13 A. (A) THE STRUCTURE DIAGRAM AND (B) THE HER POLARISATION CURVE OF
NI3(NI3•HAHATN)2 MOFS. (C) CURVES OF FREE ENERGY .(148) COPYRIGHT 2020,
WILEY-VCH. B. (A) CUCO-CAT STRUCTURE SCHEMATIC DIAGRAM. (B) AN EXCESS
OF 100 MA CM− 2 OVERPOTENTIAL. (C) ΔGH* DETERMINED USING DFT. (D) THE H2O
ADSORPTION ENERGY ON THE MATERIALS' SURFACE FOR HER. (150) COPYRIGHT
2020, WILEY-VCH. C. (A) THE CU-MOF STRUCTURAL DIAGRAM. (B) CU K-EDGE

EXAFS SPECTRA FOURIER TRANSFORM CURVES FOR FE(OH)X@CU-MOF NBS. (C)
THE LSV CURVE. (D) CU1-O4 AND CU1-O2 CENTRES' VARIATION CURVE FOR THE FREE
ENERGY OF H* ADSORBED AT CU SITES.(149) COPYRIGHT 2021, AMERICAN
ASSOCIATION FOR THE ADVANCEMENT OF SCIENCE. ................................................ 42

FIGURE 14 OVERPOTENTIALS OF THE ELECTROCATALYSTS WITH REPORTED HER ACTIVITY
IN MOFS. ................................................................................................................. 45
FIGURE 15 TAFEL SLOPE OF THE MOF ELECTROCATALYSTS CLAIMED TO BE ACTIVE BY

HER. ........................................................................................................................ 45
FIGURE 16 INITIAL CHEMICALS FOR MOFS SYNTHESIS ................................................... 50
FIGURE 17 POWDER OF PREPARED CO-MOF ELECTROCATALYST .................................... 51
xiii
FIGURE 18 POWDER OF PREPARED FE-MOF ELECTROCATALYST ..................................... 51
FIGURE 19 CO-MOFS AFTER CALCINATION BY CVD DEVICE. ........................................ 52
FIGURE 20 INK OF DIFFERENT MOF TYPES...................................................................... 54
FIGURE 21 FTIR SPECTRA OF CO.MOF SAMPLE ............................................................. 58
FIGURE 22 XRD PATTERN OF BIM, CO-MOF, AND FE-MOF SAMPLES ........................... 59
FIGURE 23 POLARIZATION CURVE COMMERCIAL PT, CO.MOF, GCE ELECTRODE ............ 61
FIGURE 24 TAFEL PLOT OF CO.MOF COMMERCIAL PT CATALYST, AND GCE ELECTRODE
SYNTHESIZED CATALYST ........................................................................................... 63
FIGURE 25 EIS MEASUREMENT FOR -CO.MOF SYNTHESIZED CATALYST AT DIFFERENT

OVERPOTENTIAL POINTS. .......................................................................................... 65
FIGURE 26 EIS MEASUREMENT FOR -COMMERCIAL PT CATALYST, CO.MOF, FE.MOF, AND

CO.FE.C.MOF/CO.FE(A) SYNTHESIZED CATALYSTS AT STATIC OVERPOTENTIAL
POINTS. ..................................................................................................................... 66
FIGURE 27 CO.MOF POLARIZATION CURVES BEFORE AND AFTER 100 CYCLES ............... 67
FIGURE 28 POLARIZATION CURVE COMMERCIAL PT, CO.MOF, /FE ,CO.C.MOF,
CO.C.MOF GCE ELECTRODE .................................................................................. 69
FIGURE 29 FTIR SPECTRA OF FE.MOF SAMPLE .............................................................. 70
FIGURE 30 XRD PATTERN OF BIM, CO-MOF, AND FE-MOF SAMPLES ........................... 71
FIGURE 31 POLARIZATION CURVE COMMERCIAL PT, FE.MOF, GCE ELECTRODE............. 73
FIGURE 32 TAFEL PLOT OF FE.MOF SYNTHESIZED CATALYST, COMMERCIAL PT CATALYST,
, AND GCE................................................................................................................ 75
FIGURE 33 EIS MEASUREMENT FOR -FE.MOF SYNTHESIZED CATALYST AT DIFFERENT
OVERPOTENTIAL POINTS. .......................................................................................... 77

CO.FE.C.MOF/CO.FE SYNTHESIZED CATALYSTS AT STATIC OVERPOTENTIAL POINTS.78
FIGURE 35 FE.MOF POLARIZATION CURVES BEFORE AND AFTER 100 CYCLES ................ 79
FIGURE 36 FTIR SPECTRA OF CO.FE.C.MOF/CO.FE(A) SAMPLE. .................................. 80
FIGURE 37 POLARIZATION CURVE, CO. FE.MOF(A) CO. FE.C.MOF/FE. CO(A),
COMMERCIAL PT, GCE ELECTRODE .......................................................................... 83
FIGURE 38 TAFEL PLOT OF CO. FE.C.MOF/FE. CO(A) SYNTHESIZED CATALYST,

COMMERCIAL PT CATALYST, AND GCE ELECTRODE. ................................................. 84
xiv
FIGURE 39 EIS MEASUREMENT FOR - CO. FE.C.MOF/FE. CO(A) SYNTHESIZED CATALYST
AT DIFFERENT OVERPOTENTIAL POINTS. .................................................................... 86

CO.FE.C.MOF/CO.FE SYNTHESIZED CATALYSTS AT STATIC OVERPOTENTIAL POINTS.86
FIGURE 41 CO. FE.C.MOF/FE. CO(A) POLARIZATION CURVES BEFORE AND AFTER 100
CYCLES ..................................................................................................................... 87
FIGURE 42 POLARIZATION CURVE, CO. FE.MOF(B) CO. FE.C.MOF/FE. CO (B),

COMMERCIAL PT, FE.MOF, GCE ELECTRODE ........................................................... 89
FIGURE 43 POLARIZATION CURVE FOR PT, CO.MOF, CO.FE.C.MOF/CO.FE (A),

CO.C.MOF, CO.C.MOF/FE. CO, CO.FE.C.MOF/FE. CO(B), CO. FE.MOF(B),
CO.FE.C.MO(A), GCE. ........................................................................................... 91
FIGURE 44 TAFEL SLOPE VALUES FOR PT, CO.FE.MOF/FE.CO (A), FE.MOF, CO.MOF . 92
FIGURE 45 EIS MEASUREMENTS FOR PT, CO.MOF, FE.MOF, CO.FE.MOF/FE.CO (A) ... 93
FIGURE 46 THE OVERPOTENTIAL OBTAINED VALUES FOR SYNTHESIZED MOFS TYPES AND
TAFEL SLOPE ............................................................................................................ 93
xv
LIST OF TABLES
TABLE 1 DIFFERENT WATER ELECTROLYSIS TECHNOLOGIES: ADVANTAGES AND

DISADVANTAGES, EFFECTIVENESS, AND TEMPERATURE OF OPERATION (50-52) ........11
TABLE 2 ADVANTAGES AND DISADVANTAGES OF MOFS SYNTHESIS METHODS (95-97)... 23

TABLE 3 IMPROVING MOF STABILITY: APPROACHES AND APPLICATIONS. ....................... 32
TABLE 4 HER PERFORMANCES OF MOF-BASED ELECTROCATALYSTS (GCE: GLASSY
CARBON ELECTRODE; CC: CARBON CLOTH; CFP: CARBON FIBER PAPER; FTO:
FLUORINE-DOPED TIN OXIDE; NF: NI FOAM). (137) .................................................. 44
TABLE 5 BASIC TABLE FOR HER ACTIVE MOFS ............................................................. 49

TABLE 6 SUMMARY OF HER PERFORMANCE OF THE PREVIOUSLY REPORTED MOF
CATALYST ................................................................................................................. 62
TABLE 7 CO.MOF DECREASING OF THE NUMERICAL VALUES OF RCT WITH INCREASE THE
POTENTIALS. ............................................................................................................. 64

ELECTROCATALYST ................................................................................................... 74
TABLE 9 FE.MOF DECREASING OF THE NUMERICAL VALUES OF RCT WITH INCREASE THE
POTENTIALS. ............................................................................................................. 77

ELECTROCATALYST ................................................................................................... 82
TABLE 11 CO. FE.C.MOF/FE. CO(A) DECREASING THE NUMERICAL VALUES OF RCT WITH
INCREASE THE POTENTIALS. ..................................................................................... 85
TABLE 12 THE OVERPOTENTIAL OBTAINED VALUES FOR PT, FE.MOF, CO.MOF, CO.
FE.C.MOF/CO. FE (A), CO.C.MOF, CO.C.MOF/FE. CO, CO.FE.C.MOF/FE. CO(B),
CO. FE.MOF(B), CO.FE.C.MO(A) AND GCE .......................................................... 91
TABLE 13 THE OBTAINED NUMERICAL VALUES FOR EIS PARAMETERS FOR PT, FE.MOF,
CO.MOF, CO.FE.C.MOF/CO. FE(A) ........................................................................ 92
xvi
1. INTRODUCTION
1.1. Hydrogen Energy
The substitution of fossil fuels with sustainable, environmentally friendly, and cost-
effective energy sources and carriers is a critical challenge for future socio-economic
progress. In this pursuit, hydrogen is considered the most favourable energy carrier. (2).
H2, with a molar mass of 2.016 × 10-3 kg/mol, is the most abundant and lightest element
in the universe. It serves as an energy-efficient fuel source on Earth due to its high
calorific or heating value. With an energy density of 140 MJ/kg, it is the highest among
all elements by weight. Hydrogen primarily exists in compounds such as water, methane,
H2S, living organisms, and organic waste. Its environmental impact is minimal since
water is its only emission product when converted into energy. Unlike electricity,
hydrogen can be stored for later use either at a central production plant or onsite at a
refuelling station (HRS). This capability could contribute to achieving a carbon-free
energy economy.(3).
1.1.1. H2 Production
Hydrogen is the most abundant element in the universe, making up around 70% of its
composition. However, free hydrogen is not easily found on Earth and is usually
combined with other elements in compounds like water and hydrocarbons, notably
methane (CH4). Separating hydrogen from these compounds requires the use of energy
in different forms. The colour spectrum of H2 varies depending on its source or how it
was produced: 1) Black-brown (from coal), 2) Gray (hydrocarbons without carbon
capture and storage—CCS), 3) Blue (hydrocarbons with CCS), 4) Turquoise (pyrolysis),
5) Pink (nuclear powered electricity), 6) Yellow (solar energy), 7) red (high temperature
catalytic process), 8) White (naturally-occurring geological hydrogen) and 9) Green
(clean RE electricity) (Fig 1). Natural gas (NG), crude oil, coal, and water electrolysis
processes are the most commonly used sources for H2 production (4).
1
Figure 1 The spectrum of H2 production processes
1.1.2. H2 Storage
While hydrogen (H2) possesses the highest energy per mass density, approximately 120
MJ/kg, compared to other fuels, its low mass density STP at standard temperature and
pressure leads to a lower energy per volume density. This requirement has prompted the
need for advanced storage techniques.
(Fig 2) (5). Storage is crucial for ensuring the safety, transport, and usage of an H2 energy
system in both stationary and mobile applications. Research indicates that energy storage
components play a critical role in decreasing reliance on fossil fuels. Hydrogen (H2) offers
cost-effective long-term storage options through physical or material-based methods (Fig
2) (6-9).
1.1.2.1. Physical-Based H2 Storage
Pressurized hydrogen gas is widely recognized as the most established method for storing
hydrogen in various applications. Due to its very low mass density of 0.089 kg/m3, high
pressure or extremely low temperatures are required for its storage (10). The volumetric
mass and energy densities of H2 enable its transportation and storage in liquid form using
highly insulated containers. This method is particularly useful for transmitting large
quantities over long distances to temporary storage locations, minimizing the risk of boil-
off loss. Serving as a vital link between abundant renewable energy sources and end-
users, the technology for liquid H2 requires cooling to extremely cryogenic temperatures
(-253 °C), consuming around 30% of its total energy content. Cryogenic pressure vessels
2
are considered safer than compressed H2 vessels due to their smaller size and lighter
weight. Liquid H2 storage systems are typically employed for short-term usage in
applications such as automotive, air travel, and space exploration (11-13).
1.1.2.2. Material-Based H2 Storage
In general, an ideal material for storing H2 in a solid state should have the capacity to
absorb a high weight percentage and volume of H2. It should also demonstrate rapid
absorption and desorption rates at or near standard temperature and pressure (STP).
Moreover, it should be cost-effective, resistant to contamination by trace impurities,
exhibit good thermal conductivity both when charged and uncharged, require minimal
energy for preparation, be safe and reusable upon exposure to air, as well as possess the
ability to be regenerated and easily recycled (13). Metallic hydrides are formed through
the reaction of hydrogen with various metals, enabling solid-state storage at moderate
temperatures and pressures. As a result, they offer distinct safety benefits in comparison
to liquid and gaseous storage methods. Chemical H2 carriers include organic hydrocarbon
liquids and inorganic materials such as ammonia and ammonia borane (14).
One of the promising options, especially for mobile devices, is nano storage based on
adsorption techniques. For aboard applications, weight and dimension constraints dictate
that H2 must be held in compact, light vessels with high gravimetric and volumetric
storage capacities. For H2 storage in onboard systems, adsorption on porous and high
surface area nanomaterials such as metal organic frameworks, carbon nanotubes,
activated carbon, spherical carbon fullerenes, and metal-decorated carbons seems
particularly promising. (15).
3
Figure 2 H2 storage methods
1.2. Technologies For Hydrogen Production
The primary methods for producing hydrogen will be determined by the type of raw
material used: fossil fuels as opposed to renewable resources.
1.2.1. Hydrogen Production from Fossil Fuels
The most widely used methods for producing hydrogen from fossil fuels now are
pyrolysis and hydrocarbon reforming. These methods virtually enable the creation of the
required amount of hydrogen..(15)
1.2.1.1. Fossil Hydrocarbon Reforming Technologies.
The method for producing hydrogen that is most advanced is hydrocarbon reforming.
This process requires additional reactants in addition to hydrocarbons. These reactants
could be steam or oxygen, which are known as the partial oxidation reaction or steam
reforming reaction, respectively. The method is known as autothermal reforming (16).
4
1.2.1.1.1. Steam Reforming.
The high-temperature reaction that produces hydrogen and carbon oxides from a mixture
of steam and hydrocarbons is known as the steam reforming reaction. Hydrogen is
extracted by steam reforming from natural gas, and less commonly from naphtha and
liquefied petroleum gas (17). Steam methane reforming from natural gas or light
hydrocarbons is, as previously said, the most utilised hydrocarbon reformation procedure.
This process starts with the production of carbon monoxide and hydrogen, resulting in
the following synthesis gas:
(CH4 + H2O → CO + 3H2), and then through the water−gas shift reaction, carbon
monoxide is converted to carbon dioxide and additional hydrogen:
(CO + H2O → CO2 + H2) (18).
The overall methane steam reforming reaction can be represented as follows:
CH4 + 2 H2O → CO2 + 4 H2 (eq. 1)
Due to the strong endothermic nature of the reforming reaction, a significant quantity of
heat is needed. Because of this, the usual temperature range for these reactions is 800–
1000 °C (19). Considering that the conversion of methane to hydrogen requires high
temperatures.
1.2.1.1.2. Partial Oxidation.
Another strategy for steam reforming reactions is partial oxidation. Methane, heavy fuel
oil, coal, and other feedstocks might all be used in this process (15, 17). The best method
for producing hydrogen from heavy fuels like coal and oil is partial oxidation (16).
Hydrocarbon fuels can be partially oxidised, an exothermic process that produces a
combination of hydrogen, carbon monoxide, and other partially oxidised molecules (20).
This process has the benefit of extremely exothermic reactions with oxygen, which
eliminates the need for an external energy source (21), Heterogeneous catalysts are
typically used in partial oxidation processes, which are conducted at lower temperatures.
Transition-metal-based catalysts may alter oxidation states and adsorb reactants and
intermediates onto their surface, making them more affordable than noble metals and
5
appropriate for partial oxidation processes (22). The partial oxidation reaction can be
explained generally as follows:
CnHm + 1/2nO2 → nCO + 1/2m H2 (2)
The most prevalent products in this process, thermodynamically considered, are CO and
H2 above 550 °C (23), CO is a precursor to coke that can be eliminated by oxidising it to
CO2 or by causing a water-gas shift reaction that increases the production of H2.
1.2.1.2. Fossil Hydrocarbon Pyrolysis
Pyrolysis is a type of heat decomposition that takes place in the absence of oxygen., (24)
It transforms several light liquid hydrocarbons into hydrogen and elemental carbon,
according to (eq 3).
CnHm → nC + 1/2m H2 (eq. 3)
CnHm + (2n − m/2) H2 → nCH4 (eq. 4)
CH4 → C + 2 H2 (eq. 5)
The most sense to proceed with the hydrogen production in two steps when the thermal
breakdown originates from heavy residual fractions that have a boiling point more than
350 °C. These two processes are methane cracking (eq. 5) and hydrogasification (eq. 4).
Different catalysts, including metallic and carbonaceous catalysts, have been described
for this process.
1.2.1.2.1. Coal Gasification.
The process of thermochemically converting coal into gaseous products, such as carbon
monoxide and hydrogen, is known as coal gasification (25-27). In practical terms, coal
is transformed into synthesis gas at high temperatures and pressures when it is combined
with steam, oxygen, or air (28-30).
6
1.2.2. Hydrogen Production from Renewable Resources.
1.2.2.1. Hydrogen Production from Water.
The most prevalent resource for producing hydrogen is water, which, with sufficient
energy and no negative emissions, can be divided into hydrogen and oxygen (31, 32). In
its most basic form, electrolysis—the passage of an electrical current between two
electrodes—is used to divide water into hydrogen and oxygen (33). Other energy sources,
such as thermal energy (thermolysis), photonic energy (photo electrolysis), and bio
photolysis using microorganisms, can also be used to divide it (31, 34).
1.2.2.1.1. Electrolysis
One of the easiest methods for creating hydrogen from water is electrolysis. It can be
summed up as follows: two reactions occur in each electrode, the anode and cathode,
converting electrical power to chemical energy in the form of hydrogen and oxygen as
byproducts (31),(35).
Anode:
𝐴𝑡 𝑡ℎ𝑒 𝐴𝑛𝑜𝑑𝑒 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛) 2𝐻2 𝑂(𝑙) → 𝑂2(𝑔) + 4𝐻 + (𝑎𝑞)
𝐴𝑡 𝑡ℎ𝑒 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 (𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛) 4𝐻2 𝑂(𝑙) + 4𝑒 − → 2𝐻2(𝑔) + 4𝑂𝐻 − (𝑎𝑞)
𝐴𝑡 𝑡ℎ𝑒 𝑎𝑛𝑜𝑑𝑒 (𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛) 2𝐻2 𝑂(𝑙) → 2𝐻2(𝑔) + 𝑂2 (𝑎𝑞)
Water electrolysis can be done using a variety of technologies, such as solid oxide
electrolysis, proton-exchange membrane electrolysis, and alkaline water electrolysis (36,
37). A gas separator is necessary for alkaline water electrolysis in order to prevent the
combination of the gas products. It makes use of non-noble metal electrodes (such as
nickel) and concentrated lye as the electrolyte. Humidified polymer membranes are used
as the electrolyte in proton-exchange membrane electrolysis, while noble metals like
platinum or iridium oxide are used as the electrocatalysts. T For both technologies, the
operating pressure can be adjusted to 30 bar, and the operating temperature can be
adjusted between 50 and 80 °C. Conversely, solid oxide electrolysis increases the heat
demand by converting water into hydrogen and oxygen at temperatures between 700 and
7
900 °C. Because of their lower initial costs and longer unit lifetimes, alkaline water
electrolysis and proton-exchange membrane electrolysis are therefore more likely to be
widely used technologies (36).
1.2.2.1.2. Thermolysis
Thermolysis is a thermochemical process that splits water into hydrogen and oxygen by
heating it to extremely high temperatures. Although this process seems simple,
temperatures exceeding 2500 °C are necessary for the water to decompose (33, 38).
In contrary to thermolysis, thermochemical water-splitting cycles generate both H2 and

O2 in separate phases at lower maximum operating temperatures (often below 1000 °C),
preventing their recombination and obviating the necessity for expensive and high-
temperature downstream gas separation (38).
1.2.2.1.3. Photo Electrolysis
By combining the electrolysis process with solar energy absorption in a single unit, photo
electrolysis splits water and adds to the sustainability of the energy supply. In addition to
solar energy, electricity is needed to support this process; as a result, photonic and
electrical energies are transformed into chemical energy in the form of hydrogen (30).
By absorbing photons with energy higher than the band gaps of semiconducting
photoelectrodes, holes and electrons are produced in photoelectrochemical cells, enabling
water photo electrolysis (39).
The kind of material that absorbs photons, its surface characteristics, crystalline structure,
resistance to corrosion, and reactivity all affect how well this system works (30).
1.2.2.1.4. Bio Photolysis.
A photonic-driven biochemical process called "bio photolysis" produces hydrogen from

water (40). In direct bio photolysis, an anaerobic environment of microorganisms uses
the catalytic activity of the hydrogenase enzyme to split a water molecule into oxygen
and hydrogen ions by photosynthesis (41).
8
1.2.2.2. Hydrogen Production from Biomass.
Plant and animal components are the source of biomass, a renewable main energy source
(15), such as crop residue, animal waste products, microalgae, municipal solid waste,
and forest residues (42, 43), They are seen as possible sources of chemical feedstocks
and fuels.
Biomass can be converted into hydrogen primarily through two processes:

thermochemical and biological. The thermochemical process yields more hydrogen and
is typically much faster than the biological approach (44).
1.2.2.2.1. Biological Processes
The two primary biological mechanisms used to produce hydrogen are photo fermentative
and dark fermentative processes (33, 45). Anaerobic bacteria are employed in dark
fermentative processes on substrates high in carbohydrates, in the absence of light, and
in anoxic circumstances. This produces the original biomass in H2, organic acids, and
CO2 (44, 46, 47). Enzyme-mediated biochemical processes at room temperature and
pressure produce biohydrogen during the dark fermentation process (45, 47).
Conversely, in photo fermentation, which occurs in anaerobic environments,

photosynthetic bacteria utilise light from the sun to break down tiny organic molecules in
biomass. This process produces H2 and CO2 as byproducts, which enable the generation
of hydrogen from a variety of substrates (48, 49).
1.3. Hydrogen Production from Water Electrolysis
Because electrochemical water splitting produces hydrogen without leaving a carbon

footprint due to half-cell reactions (HER and OER) at the cathode and anode, respectively,
it is one of the greenest methods for producing hydrogen. Equation (eq. 1) depicts the
ultimate electrochemical breakdown of H2O into H2 and O2 (by-product).
4𝐻 + + 4𝑒 − → 2𝐻2 (𝐻𝐸𝑅) 𝑎𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒
2𝐻2 𝑂 → 𝑂2 + 4𝐻 + + 4𝑒 − (𝑂𝐸𝑅) 𝑎𝑡 𝐴𝑛𝑜𝑑𝑒
9
2𝐻2 𝑂 → 2𝐻2 ↑ +𝑂2 ↑
Wind, solar, and biomass energy are examples of sustainable energy sources that are used
in electrolysis to give direct current power. However, due to financial difficulties and the
high cost of the process's constituent parts (electrocatalysts), only 4% hydrogen has been
produced using the water electrolysis method. These costs are anticipated to rise soon as
a result of increased use of renewable resources. The energy needed for the decomposition
reaction varies depending on the water's temperature and pressure. Gibbs free energy
defines the minimal water decomposition voltage required as a function of temperature
and pressure (Eq. (2)) (2). ΔG = ΔH -TΔS where, ΔG = Gibbs free energy of water
formation, TΔS = Entropy changes of water formation (multiplied by temperature, T) and
ΔH = Enthalpy change of water formation (50).
1.3.1. Classification Of Water Electrolysis Technologies
Water electrolysis can be classified into three main types depending on the types of
electrolytes, operating temperatures, and ionic agents. As shown in (Fig. 3) , the three
types of electrolysis technologies are (a) alkaline electrolysis, (b) solid oxide electrolysis
and (c) proton exchange membrane electrolysis. Table 2 lists the three types of water
electrolysis technologies.
Figure 3 Schematic illustration of a. alkaline electrolysis, b. solid oxide electrolysis, c.

proton exchange membrane electrolysis
10
Energy
Water electrolysis Operating temperature
Advantages Disadvantages efficiency
process (C)
(%)
Traditional
technology Low current density
affordable (A/cm2), carbonated
Alkaline water
electrocatalyst. deposit on electrodes, 40-90 70-80
electrolysis (AWE)
commercially and electrolyte that is
available non- prone to corrosion
noble catalyst
high pressure Ceramic framework's

reaction, limited durability causes
Solid-oxide
increased brittle setup in heavy 500-1000 90-100
electrolysis (SOE)
output, non- system design for lab-
noble catalyst scale production.
The current
density is high
(A/cm2).
Precious catalysts are
compact and
mostly applied. The
Proton exchange small-scale
nature of the electrolytic
membrane experimental 20-100 80-90
media is corrosive. less
electrolysis (PEME) structure of
robust experimentally
systems. high
expensive
H2 gas purity
and dynamic
operation
Table 1 Different water electrolysis technologies: advantages and disadvantages,

effectiveness, and temperature of operation (50-52)
11
1.3.2. Electrochemical Reactions in Water Electrolysis
There are two electrochemical half-reactions that make up the overall reaction in the
catalytic process of water electrolysis. The hydrogen evolution reaction (HER) at the
cathode and the oxygen evolution reaction (OER) at the anode are these two reactions
(53) (54, 55).
For the three types of water electrolysis, water is oxidised at the anode to create O2, as
indicated by reactions (eq. 1) (eq. 3):
2𝐻2 𝑂 → 𝑂2 + 4𝐻 + + 4𝑒 −
(Electrolysis of proton exchange membranes at low temperatures) (eq. 1)
4𝑂𝐻 − → 2𝐻2 𝑂 + 𝑂2 + 4𝑒 −
(Low-temperature alkaline electrolysis) (eq. 2)
2𝑂2− → 𝑂2 + 4𝑒 −
(Electrolysis of solid oxide at high temperatures) (eq. 3)
Water is reduced to create H2 at the cathode, as shown by the reactions (eq. 4) – (eq. 6)
for the three different forms of water electrolysis:
2𝐻 + + 2𝑒 − → 𝐻2
(Electrolysis of proton exchange membranes at low temperatures) (eq. 4)
2𝐻2 𝑂 + 2𝑒 − → 𝐻2 + 2𝑂𝐻 −
(Alkaline electrolysis at low temperatures) (eq. 5)
𝐻2 𝑂 + 2𝑒 − → 𝐻2 + 𝑂2
(Solid oxide electrolysis at high temperatures) (eq. 6)
The overall reaction of the three electrolysis processes can all be expressed as Eq. (7)
with a standard cell voltage of 1.23 V:
12
2𝐻2 𝑂 → 𝑂2 + 2𝐻2 (eq. 7)
The standard cell voltage of 1.23 V should be noted here because it only applies to
standard thermodynamic conditions (1.0 atm and 25 °C). It does not apply to other
situations. The larger overpotential of the OER at the anode than that of the HER at the
cathode indicates that, in terms of the kinetics of the OER and HER, the OER is typically
significantly slower than the HER. Nonetheless, the OER and HER overpotentials may
both be a factor in the total energy efficiency of water electrolysis being limited (51, 56-
58). Using electrocatalysts in the electrolysis process increases both OER and HER
kinetics, which in turn reduces overpotentials and improves energy efficiency. Generally,
OER and HER electrocatalysts are put onto their respective electrodes.
1.3.3. Electrocatalyst Used in Electrolysis.
A catalyst that takes part in electrochemical reactions is known as an electrocatalyst. A

particular type of catalyst known as an electrocatalyst works at electrode surfaces or, more
frequently, at the electrode surface itself. Heterogeneous electrocatalysts, like platinized
electrodes, are possible. (59) Soluble homogeneous electrocatalysts aid in the
transmission of electrons between the electrode and reactants and/or enable a chemical
transformation in between that is represented by an overall half-reaction (Fig 4) (60). A
catalyst is, essentially, an agent that speeds up a chemical reaction without getting
consumed by it. A catalyst reduces the activation energy needed for a chemical reaction
to occur thermodynamically. A catalyst that modifies an electrochemical reaction's
activation energy is known as an electrocatalyst (60) . In electrochemical processes, the
potential, or voltage, at which a reaction takes place is connected to the activation energy.
Therefore, the voltage at which oxidation and reduction reactions are detected is
commonly altered by electrocatalysts (61). As an alternative, one way to conceptualise an
electrocatalyst is as an agent that helps to promote a certain chemical reaction at an
electrode surface (62). Favourable interactions at an electrode surface improve the
likelihood of electrochemical transformations occurring, lowering the potential required
to effect these transformations since electrochemical reactions occur when electrons are
transported from one chemical species to another (62). Three figures of merit can be used
to assess electrocatalysts: selectivity, stability, and activity. Quantitative evaluation of
electrocatalyst activity can be achieved by measuring the amount of current density
13
generated, and consequently the rate of reaction, at a specific applied potential. The Tafel
equation provides a description of this relationship (60). The capacity of catalysts to
tolerate the potentials at which transformations are taking place is essential for evaluating
the stability of electrocatalysts. The term "selectivity" describes an electrocatalyst's
preference for interacting with specific substrates and producing a single product (60). A
selectivity coefficient, which contrasts a material's reaction to a targeted analyte or
substrate with its response to other interferents, can be used to quantitatively evaluate
selectivity (63).
Figure 4 A flow chart classifying the types of materials that can serve as
electrocatalysts, including homogeneous and heterogeneous electrocatalysts.
1.3.3.1. Homogeneous Electrocatalysts
One that is present in the same phase of matter as the reactants is known as a
homogeneous electrocatalyst. An example of this would be a water-soluble coordination
complex that is catalysing an electrochemical conversion in solution (64, 65). Although
not used commercially, this technique is interesting for study.
14
1.3.3.1.1. Enzymes
There are certain enzymes that are electrocatalysts (66). The MoFe cluster-containing
enzyme nitrogenase can be used to fix atmospheric nitrogen or change nitrogen gas into
compounds like ammonia. The technique is made much more efficient by immobilising
the protein on an electrode surface and using an electron mediator (67). The ease of
electron transport between the enzyme's active site and the electrode surface is a major
factor in bio electrocatalysts' efficacy.
1.3.3.2. Heterogeneous Electrocatalysts
An electrocatalyst that is heterogeneous is one that is found in a different phase of matter

than the reactants; an example of this would be a solid surface that is catalysing a process
in solution. The materials used as heterogeneous electrocatalysts are displayed above in
green. The reaction kinetics are dependent on the catalyst and the electrolyte as well as
the interface between them because heterogeneous electrocatalytic reactions require an
electron transfer between the solid catalyst, which is usually a metal, and the electrolyte,
which can be a liquid solution, polymer, or ceramic that can conduct ions (62). Selectivity
and rate of the reaction are two characteristics that are determined by the electrocatalyst
surface type (62).
1.3.3.2.1. Bulk Materials
Certain bulk materials, like platinum metal, can undergo electrocatalysis near their
surface. Hydrogen synthesis from the breakdown of methanol has been achieved by the
use of bulk gold metal surfaces (60). Conventionally, inert bulk metal electrodes like
iridium or platinum are used for water electrolysis (68). An electrocatalyst's activity can
be adjusted chemically; this is often accomplished by alloying two or more metals. This
is because of a shift in the electronic structure, particularly in the d band, which is thought
to be in charge of noble metals' catalytic qualities (69).
15
1.3.3.2.2. Nanomaterials
1.3.3.2.2.1. Nanoparticles
Numerous nanoparticle materials have been shown to facilitate a range of electrochemical

processes (70). Although none have been made available for purchase. The surface strain
as well as the size and form of these catalysts can be adjusted (71). Since the specific
surface area increases as the average particle size drops, the adoption of tiny catalyst
powders was motivated by the desire to minimise catalyst costs for electrochemical
processes. As an example, the design of most popular electrolysers is based on a
polymeric membrane that has been electrocatalysis with platinum nanoparticles (also
known as platinum black) (68).
1.3.3.2.2.2. Carbon-Based Materials
Materials based on graphene and carbon nanotubes can be utilised as electrocatalysts.

(24) Many chemical species can be adsorbed onto the carbon surfaces of carbon
nanotubes and graphene, which can facilitate specific electrocatalytic reactions (62).
Additionally, they make good electrode materials due to their conductivity (62). Because
of their extremely large surface area, carbon nanotubes maximise the number of surface
sites available for electrochemical reactions (72). Moreover, graphene can be used as a
building block to create composites including different types of nanomaterials, like
single-atom catalysts (73). Carbon-based materials have the ability to perform metal-free
electrocatalysis in place of metal electrodes due to their conductivity (74).
1.3.3.2.2.3. Framework Materials
MOFs, particularly conductive ones, have the potential to function as electrocatalysts in

several processes, including water splitting and CO2 reduction. Potential active sites are
offered by MOFs at both organic ligand and metal centre locations (75). Additionally,
they can encapsulate different elements, such nanoparticles, or functionalize them
(75). Moreover, MOFs can be mixed with carbon-based substances to create
electrocatalysts (76).
16
1.4. Metal−Organic Frameworks
1.4.1. Introduction
MOFs, or metal-organic frameworks, are a broad class of crystalline materials that have
extremely high porosity (free volume up to 90%) and large interior surface areas (more
than 6,000 m2/g). MOFs are interesting for potential uses in clean energy because of these
characteristics as well as the remarkable degree of variability for both the organic and
inorganic components of their structures. These uses include, most notably, serving as
high-capacity adsorbents to meet a variety of separation requirements and as storage
media for gases like hydrogen and methane. Further uses in thin-film electronics,
membranes, catalysis, and biological imaging are becoming more and more significant
(77). Fundamentally, MOFs represent the power of fusing organic and inorganic
chemistry—two fields that are sometimes seen as distinct from one another—and the
beauty of chemical structures. According to Yaghi et al., MOFs are porous structures
made of metal ions and organic linkers or bridging ligands formed through coordinative
bonding (Fig 5) (78). Secondary-building units (SBUs) or metal-containing units are
anchored with organic linkers by coordination to generate MOFs. The organic units, also
known as linkers or bridge ligands, are made up of carboxylates, or anions, such as
phosphonate, sulfonate, and heterocyclic compounds. These result in open frameworks
with remarkable properties like stable frameworks, large surface areas, pore volumes, and
permanent porosity. Long organic linkers give MOFs a lot of storage space and a lot of
adsorption sites, which contribute to their porosity. Additionally, they possess the capacity
to consistently alter and customise their pore structure (78). The synthesis of MOF-5
(Zn4O(bdc)3, bdc = terephthalate) and HKUST1 (Cu3(btc)2), btc = 1,3,5benzene
tricarboxylate) with high porosity and low-pressure gas sorption served as a benchmark
in the history of MOFs. This was followed by the development of MIL101, which had
high chemical stability, and MOF-74 (Zn2(dhbdc), dhbdc = 2,5dihydroxy1,4benzene
dicarboxylate), which had low pressure CO2.
17
Figure 5 Illustration of MOF’s building blocks and resulting porous, crystalline
structure.
1.4.1.1. Chemistry
MOFs are made up of both organic and inorganic components. Phosphonate, sulfonate,
and heterocyclic chemicals are examples of carboxylates, or anions, that make up the
organic units (linkers/bridging ligands). The metal ions or clusters known as SBUs are
the inorganic units. The coordination number (framework topology), the coordination
geometry of the metal ions, and the makeup of
the functional groups all influence its geometry
(78). By examining their framework topology,
which characterises the general network
connectedness of the MOF building units (79).
Several SBU geometries, including the square
paddlewheel with four points, the trigonal
prism with six points, the octahedron with six
points, and the triangle with three points, have
been discovered in MOF structures (Fig 6).
Figure 6 MOFs resulting from different metal nodes and bridging ligands.(78).
18
1.4.2. MOFs Synthesis
The creation or breaking of bonds requires energy, and as the synthesis of MOFs involves
the bonding of metal oxides and organic linkers, this phenomenon also applies to the
synthesis of MOFs. The primary goal of MOF synthesis is to produce distinct inorganic
building blocks that do not decompose organic linkers. Appliances of any kind that can
provide a regulated amount of heat are appropriate for the synthesis of MOFs. Examples
of sources from which heat can be produced include ovens, microwaves, mechanical
ultrasonography, electric potential, and electromagnetic wave radiation (80). MOFs are
formed using the same reactive mixture (metal source, organic ligand, and solvent);
however, the structure varies depending on the reaction time, yield, particle size, and
shape. Consequently, the various techniques for synthesizing MOFs are crucial. A few of
the synthesis techniques are ideal for the large-scale procedure. A few techniques,
including diffusion synthesis, solvothermal synthesis, microwave synthesis, Sono
chemical synthesis, electrochemical synthesis, and iono-thermal synthesis method, are
employed in the production of MOFs (Fig. 7). The benefits and drawbacks of various
MOF synthesis techniques are listed in (Table 2).
Figure 7 Different methods of MOF synthesis, (a) Sono-chemical synthesis method, (b)
Conventional solution method, (c) Diffusion synthesis method, (d) Iono-thermal process
method, (e) Microwave synthesis method, (f) Electrochemical synthesis method, and (g)
Solvothermal synthesis method.
19
1.4.2.1. Sonochemical Synthesis
The process of applying ultrasonic as a heat source to regulate the compounds' reaction
mechanism is known as sonochemical synthesis. The word "sono" refers to
ultrasonography. (Fig. 7a). A mixture of substrate solution for the required MOFs
structure is added to a horn-shaped Pyrex reactor that has an adjustable power output and
a sonicator bar, all without the requirement for external cooling. Bubble production and
collapse happened after sonication (acoustic cavitation) produced extraordinarily high
pressure (about 1000 bar) and temperature (about 5000 K) (81, 82). This leads to the
generation of tiny crystals and heating and cooling speeds that are more than 1010 K/s
(83)
1.4.2.2. Conventional Solution Method
This process involves continually stirring a solvent containing organic ligands, metal
elements, and other raw materials for a certain period at a given temperature, as shown in
(Fig. 7b). Clear MOFs crystals are then obtained by further solvent evaporation after the
mixture has been filtered to separate the reaction products. (84)
1.4.2.3. Diffusion Synthesis Method
Liquid phase diffusion is one of the diffusion methods (85), diffusion of gel (86), and the
diffusion of gas-phase (87). The liquid phase diffusion approach dissolves organic ligands
and centre metal ions in an incompatible solvent. Metal ions and organic ligands interact
at the surface to produce MOFs crystals (88). On the other hand, MOFs crystals in the gel
phase as two branches of the group are obtained using the gel diffusion method, which
involves mixing a solution containing centre metal ions and a gel substance dispersed
with organic ligands for a specific amount of time (86). The volatile organic ligands
solution is utilised as a solvent in the gas phase diffusion procedure. MOFs are produced
when there is a sufficient reaction by mixing the solutions of organic ligands and centre
metal ions (87), (Fig. 7c).
20
1.4.2.4. Iono-Thermal Process
The ionic liquid medium is used in the synthesis of metal-organic frameworks instead of
the organic solvent medium or regular ordinary water. (Fig. 7d). (89)
1.4.2.5. Microwave Synthesis
Here, after being cleaned with deionized water, metal ion sources and organic linkers
(starting material) with a stainless-steel ball are put in a miller. When the heat source, i.e.,
microwave irradiation, is put into miller, it stirs simultaneously (Fig. 7e). The solution is
recovered and carefully filtered after 30 to 50 minutes. Afterward, the filter is added to
the ethanol solution and stirred using a magnetic stirrer. Precipitates are dried and suction-
filtered after two to three hours for analysis (90).
1.4.2.6. Electrochemical Synthesis
In comparison to the other batch, it yields a higher solid content (91). In comparison to
the other batch, it yields a higher solid content (95). An anode, a battery cell, and cathode
plates are parts of this method of production. An electrochemical media (bath) containing
organic ligands and a metal salt is submerged in the anode and cathode, (Fig. 7f).
1.4.2.7. Solvothermal Synthesis Method
When water is utilized as a solvent, the solvothermal synthesis process is also known as
a hydrothermal synthesis method. (92) . For a predetermined amount of time at a
predetermined temperature, a continuous mixture of organic ligands, metal ions, and
reaction solvent with regulators in a specific ratio is mixed inside a
polytetrafluoroethylene liner, (Fig. 7g). To initiate the reaction at a specific temperature,
the mixture is after that moved to a high-temperature reactor. The mixture is allowed to
cool to room temperature after the reaction is finished. To get rid of the contaminants, the
product is then repeatedly cleaned with a deionized solution, like water. After cleaning
the product with anhydrous ethanol or another solution at a certain temperature, pure
MOFs are obtained by vacuum drying (93, 94).
21
Synthesis
Advantages Disadvantages
methods
MOFs have both chemical and In certain systems, increasing the

thermal stability, with their reaction temperature is necessary to
Conventional
crystallinity occurring quickly achieve appropriate crystallinity and
solution
through room temperature reaction rates, but only if more inert
synthesis. ions are employed kinetically.
Under insignificant reaction

Diffusion
conditions, sensitive MOFs are Quick response time
synthesis
synthesized.
Precursors that dissolve are needed.

Regent dissolving requires heat
and/or strong reagents (acids,
organic solvents, bases). The
It is easy to obtain single
production of solvent waste is high.
Solvothermal crystals. For structural
Handling explosive or corrosive
synthesis characterisation, single-crystal
metal salts (nitrate/chloride) in the
X-ray diffraction is employed.
presence of organic liquids could be
dangerous. Reactions produce waste
mineral acids or salts (e.g., HNO2
HCI)
the quick response time and Not suitable for reagents and
rapid reaction rate. The potential solutions that are heat sensitive. It is
Microwave to regulate the size of crystals challenging to regulate the
synthesis increased yield with exceptional irradiation power in a way that
phase selectivity and purity. would alter the reaction conditions.
Small-scale artificial device use.
22
Artificial devices that use little Temperature and response time are
energy and generate little waste also its limitations since various
chemicals. devices cannot provide the same
circumstances, which eventually
hinders repeatability.
Even when room temperature

Quick, green, and energy-
synthesis is used, there are situations
Sono chemical efficient production of
when the temperature of the
synthesis nanocrystalline particles at room
synthesis near the reactive mixture
temperature.
area cannot be regulated.
Compared to batch processes, a

Only when there is guaranteed
continuous synthesis technique
continuous electrical contact
Electrochemical might have a greater solids
between the entire metallic pattern
synthesis content. can be applied as an
and the power source may MOFs
industrial technique for MOF
grow by anodic oxidation.
synthesis.
Considered to be a green
synthesis technique Modifying
the ionic liquid's composition
allows for the manipulation of
A tiny amount of residue or
Iono-thermal MOFs' physicochemical
contaminant in the ionic liquid
synthesis characteristics. high stability at
reduces its thermal stability.
temperature. Reflux condenser is
not necessary when doing
synthesis at moderate to higher
temps.
Table 2 Advantages and disadvantages of MOFs synthesis methods (95-97)
23
1.4.3. MOF Properties and Applications
The main MOFs properties and applications are exhibited and explained in following
(Fig. 8) and (table 3) (98).
Figure 8 Schematic illustration showing stable MOFs composed of metal clusters. (blue
or orange balls), organic linkers (grey lines) and dangling functional groups (green or
pink segments) for diverse applications. (98)
Improving MOF stability: approaches and applications Table 3.
MOF Properties Examples of MOF for particular

Main principle
and applications application
Large surface areas and In the process of separating CO2 from

tuneable porous flue gas produced by coal-fired power
Adsorption and structures make MOFs stations, which contains traces of Sox,
separation great options for NOx, and other pollutants along with
sorption and separation 15–16% CO2, 73–77% N2, 5–7% H2O,
of molecules. Most of and 3–4% O2. MOFs with respectable
24
the study on MOF chemical stability are needed for these
sorption and separation applications (101). Zn2+ ions were used
is concerned with gases to create three hydrophobic ZIFs with
relevant to energy, such chabazite structure by using two
as hydrogen, methane, different imidazolates as linkers..(102)
and carbon
Furthermore, stable and/or
dioxide, etc. (99, 100).
hydrophobic MOF-based materials can
More precisely, most
be used as effective adsorbents for the
realistic
removal of target compounds from
sorption/separation
aqueous solutions, the adsorption of
processes invariably
corrosive gases, and the separation of
involve environments
oil and water. To absorb corrosive and
that are saturated with
hazardous ammonia (NH3). (103-105)
water or moisture in
(106).
addition to a variety of
other unfavourable
circumstances.
MOFs are an excellent A Zr-based MOF called PCN-225 was

platform for described by Jiang et al. as stable for
fluorescence sensing due 12 hours in aqueous solutions with a
to their tuneable pH range of 1–11 (110). By utilising
structures and PCN-225's excellent stability and pH-
Fluorescence fluorescence. The dependent fluorescence, this MOF was
sensing resulting MOFs' able to distinguish between aqueous
fluorescence properties solutions with varying pH values
can be largely controlled between 0 and 10.2.
by adjusting the metal
ions and organic linkers.
In particular, the MOFs' Based on the extremely stable PCN-
composition, structure, 222.190, Deibert et al. created a
functional groups, reversible colorimetric fluorescence pH
25
interaction sites, and sensor.
other elements may be PCN-222, which is purple in colour,
sensitive to outside turned green when exposed to an
stimuli including aqueous solution with a pH of zero.
solvents, ions, This colorimetric response was
temperature, and repeatable and reversible. to identify
pressure. MOFs can be and eliminate organic contaminants
employed as sensors or from wastewater, including organic
probes because of their explosives and medicines. (111)
sensitivity to external
stimuli through
fluorescence. To achieve
this, it is necessary to
preserve the MOF sensor
frameworks under
various testing settings
while the fluorescence
changes (107-109).
Due to its high surface Cu-TCA, which is made of

area, tuneable pore tricarboxytriphenyl amine (TCA)
widths, flexible physical linkers and Cu2(O2CR)4 paddlewheel
and chemical properties, units, is a prime example of biosensing.
Biological and and other attributes, Cu (II) complexes and NO acted in
medical multifunctional organic concert to transform Cu2+ ions into Cu+
applications filters, or MOFs, have ions, which in turn caused the
many uses in the luminescence from Cu-TCA to recover
biological and medical in aqueous solutions. Cu-TCA's high
domains, including as emission made it an ideal choice for
drug release, biosensing, biological imaging of NO in living
and biomimetic cells. (115)
catalysis. For these uses,
26
MOFs with remarkable
chemical stability are
crucial. They should be
very resistant to
hydrolysis/collapse in
physiological settings
where they would be
expected to function,
such as intestinal
alkalinity, stomach
acidity, and peristalsis in
the oesophagus,
stomach, and intestines
(112-114).
Because of their
customizable structures,
MOFs have attracted Strong acids like H2SO4 easily release
significant attention in protons, therefore H2O2 oxidised UiO-
the field of proton 66(SH)2 to produce UiO-66(SO3H)2,
conductivity over the which had SO3H groups covalently
past few decades .(116, attached to the framework and
Proton 117). In contrast to other significantly improved proton
conductivity porous materials, MOFs' conductivity. UiO-66(SO3H)2
proton conduction may demonstrated its excellent stability
be readily regulated by over a 96-hour period, exhibiting an
adjusting the surface exceptional protonic conductivity of
structure's acidity and 8.4 × 10-2 S cm-1. This was measured at
hydrophilicity. The basic 80 °C and 90% relative humidity.(120).
definition of MOF
stability as proton
conductors, in theory, is
27
their capacity to remain
stable over an extended
period of time at various
humidity and/or
temperature levels. It's
essential to remember
that, in accordance with
the Grotthuss or proton-
hopping mechanism,
proton transport mostly
depends on the creation
of hydrogen-bonded
water networks in the
cavities of MOFs. As a
result, creating MOFs
with high chemical
stability through design,
synthesis, and
modification will offer a
great starting point for
researching their proton-
conducting
characteristics. (116,
118, 119)
Lewis acidic sites for MOF catalysts based on M3 For Lewis

Catalysis
catalysis have been acid catalysis, the MIL-series (MIL-47,
(Lewis Acid shown to function as co- MIL-53, MIL-88, MIL-100, and MIL-
Catalysis) ordinately unsaturated 101) is one of the most extensively

metal sites in MOFs. In researched classes of MOFs with
gas phase catalysis, the trivalent metals (e.g., Al3+, Cr3+, and
coordinated solvent Fe3+). The produced metal sites in
28
molecules can be MIL-100(Fe) can function as Lewis
eliminated by exposing acidic sites for catalytic processes by
these sites through eliminating terminal water molecules
activation procedures on the [Fe3(µ3-O)(OH)( H2O)2(COO)6]
like heating and cluster (121).
evacuation. By
substituting coordinated
solvent molecules with
substrate molecules in
solution, the active metal
sites can interact with
the substrate. The metal
nodes provide intrinsic
Lewis acidic sites for
stable MOFs based on
high-valency metals and
carboxylates. Research
has demonstrated that
MOFs' Lewis acidic
sites can catalyse
several different
processes, including the
cyanosilylation of
aldehydes (121).
Redox Catalysis
Linkers with As an example, PCN-222 was used as a
functionalities as biomimetic oxidation catalyst with
catalysts. Some stable various metalloporphyrin
MOFs (such those based compositions. To determine PCN-222's
on Al3+ and Zr4+) have catalytic activity, three substrates were
limited uses as redox used: pyrogallol, 3,3,5,5-
catalysts due to their
29
redox inertness. Metallo- tetramethylbenzidine, and o-
linkers are one way to phenylenediamine. (122).
functionalize stable
MOFs for redox
catalysis (122).
Beyond their intrinsic For instance, triflic anhydride and

Brønsted Acid Lewis acidic sites, stable sulfuric acid can be used to
Catalysis MOFs can also be functionalize MIL-53(Cr) and MIL-
functionalized with 101(Cr) using sulfonic acid (126).
Brønsted acid catalysts, They performed exceptionally well as
increasing the variety of catalysts for esterifying n-butanol with
catalytic activities that acetic acid.
can be achieved. Recent
studies have examined
several processes, such
as acetalization,
isomerization,
esterification, and
dehydration, using stable
MOFs that include
Brønsted acids.
Covalently attaching
Brønsted Acidic groups
to organic ligands is one
method of incorporating
them into MOFs (123)
(124) (125) (126) (127).
30
One method that shows In this domain. The only photocatalysts
promise for directly that have been thoroughly investigated
Photocatalysis
converting solar energy are Ti-based MOFs containing
into useful and pure photoactive Ti-oxo clusters. (131).
chemical energy is
photocatalysis (128)
(129).
Because of the organic

linkers' or the metal
centres' ability to absorb
light, MOFs have
Mo-based catalysts, such as MoS2 and
garnered a lot of
Mo2C, are among the fascinating
attention as intriguing
classes of materials that they belong to
catalysts.
(130).
Even though Pt-based

As atomically specified, nanoscopic
Electrocatalysis
catalysts are now the
catalysts for the electrochemical
greatest electrocatalysts,
reduction of CO2 in aqueous solution,
their prohibitively high
Yang and colleagues developed thin
cost and scarcity greatly
films of nanosized MOFs. Cobalt
hinder their widespread
oxidation state during the reaction was
practical use. The use of
revealed by in situ spectra
effective, affordable
electrochemical measurements, which
catalysts in place of
also showed that most catalytic sites in
pricey Pt-group metals
this MOF are redox-accessible during
offers great potential for
catalysis from Co(II) to Co(I).(132).
sustainable energy
devices. Because of their
versatility, MOFs have
31
the potential to be
among the many
nonprecious catalysts
that are extremely
effective for significant
electrochemical
reactions. Because of
their comparable
electrical structures
(130).
Table 3 Improving MOF stability: approaches and applications.
1.4.4. Applications of MOF Electrocatalysts In Overall Water Electrolysis
The two half reactions that make up water splitting are the OER at the anode and the HER
at the cathode. To achieve high catalytic efficiency, OER and HER compatibility and
reaction kinetics are essential. It is imperative to develop an electrocatalyst with high
activity in both OER and HER processes at a reasonable cost. Consequently, there has
been an overwhelming development trend in the application of HER/OER bifunctional
electrocatalysts in total water solution plants.
1.4.4.1. MOF-Based Overall Water Splitting Electrocatalysts.
The development of non-noble metal electrocatalysts is very critical because of the issues
with limited earth abundance, high cost, and poor stability. Strong pore structure and large
surface area of MOFs provide unique advantages for electrocatalytic reactions such as
OER and HER. (133). Additionally, within a particular MOF structure, the chemical
makeup and connecting units of the MOFs can be altered to create a synergistic
combination of capabilities for electrocatalysis. As a result, a promising dual function
electrocatalyst is the transition metal MOF electrocatalyst. NF can be used as an
electrocatalyst carrier to get over MOF materials' electrical conductivity flaw. This results
from NF's large surface area, excellent electrical conductivity, and robust mechanical
strength. Additionally, the microporous channel in NF helps the mass transfer mechanism
32
in the electrocatalytic process. Consequently, growing MOF electrocatalyst in-situ on NF
is a useful method for producing an electrocatalyst that is both effective and long-lasting
by accelerating the carrier transport speed between the catalyst and support.
Using 2-amino terephthalic acid (H2BDC-NH2) as an organic linker, Raja et al.

synthesized NH2MIL88B(Fe2Ni) MOF (NFN-MOF) on NF surface. This unique, nano
porous, water-stabilized amino-functionalized bimetal MOF was used in alkaline water
electrolysis (Fig. 9a). At a current density of 10 mA cm2-, NFNMOF/NF showed ultra-
low overpotentials of 87 and 240 mV for HER and OER in an alkaline medium. By
observing the device's entire water breakdown process in Fig. 9b–c, one can examine the
overall water performance of NFN-MOF/NF in 1 M KOH. A significant amount of
hydrogen and oxygen bubbles were emitted from the cathode and anode electrodes,
respectively. The experiment yielded a current density of 10 mA cm2- at a voltage of only
1.56 V for the NFNMOF/NF//NFN-MOF/NF couple, which was compatible with the
combined potential results of HER and OER. (Fig. 9d). Its voltage was significantly lower
than Pt-C/NF//IrO2/NF (1.68 V), as Fig. 9e illustrates. Its voltage was significantly lower
than Pt-C/NF//IrO2/NF (1.68 V), (133).
Figure 9 (a) The NH2-MIL-88B(Fe2Ni)-MOF / NF synthetic process schematic

diagram. Using NFN-MOF/NF as the anode and cathode in a whole cell setup: (b)
when operating at a high current density and (c) following such operation. (d) The total
water electrolysis performance LSV curve, and (e) the accompanying Tafel plots.(133)
Copyright 2018, WILEY-VCH. Schematic diagram of NH2-MIL-88B(Fe2Ni)-MOF /NF
synthetic process.
33
1.4.4.2. MOF-Derived Overall Water Splitting Electrocatalysts.
MOFs have drawn a lot of interest lately as self-sacrificing templates and/or precursors
for the synthesis of bifunctional electrocatalysts for materials made of porous carbon and
similar nanostructures. Electrocatalyst endurance can be increased by encasing active
metal-compound NPs in a carbon shell, which not only shields them from harsh
environments but also inhibits agglomeration. (134). Co-based compounds, which are one
of the traditional examples of transition metal compounds, have been widely employed
as HER and OER electrocatalysts over the past several years. Examples of these
compounds include cobalt oxides, cobalt sulfides, and cobalt phosphides. For example,
Huang and colleagues used an ultrahigh-speed and high-energy microwave pyrolysis
approach to manufacture a highly efficient self-supporting MOF-derived electrocatalyst
(Co-NC/CF). (Fig. 10a). Co-NF/CF is a nanosheet array structure, and the vertically
arranged carbon nanotubes on its surface are conducive to enhancing the mass transfer
ability of the electrocatalytic process. As seen in (Fig. 10b-d), Co NC/CF can achieve the
current density of 10 mA cm-2 of HER and OER with just an overpotential of 157 and 246
mV, respectively. Electron transport from Co metal to graphite carbon layer causes the P
conjugate delocalization of the piezoelectric pz orbital partially filled by C atom in the
HER process. Its electrocatalytic activity is increased and its binding ability with the
intermediates is improved as a result, leading to noticeable electronic states at the Fermi
level (Fig. 10c). The energy barrier for the subsequent steps in the OER process is
downward if the rate-limiting step of the maximum potential step at the equilibrium
potential (U0 = 0.402 V) is passed. From a thermodynamic perspective, the process can
happen on its own (Fig. 10e). Theoretical and experimental data analysis leads to the
conclusion that Co-NC/CF should have electrocatalytic performance comparable to
RuO2-CF. According to the overall results of its water electrolysis test, Co-NC/CF only
requires 1.647 V at 10 mA cm-2 to reach its potential. Overall, the recently created Co-
NC/CF electrocatalyst exhibits strong HER/OER bifunctional catalytic activity, long-
lasting stability, and enormous practical potential (135).
34
Figure 10 (a) Schematic diagram of the preparation route of Co-NC/CF. The LSV curves
diagram of (b) HER and (d) OER in 1 M KOH. (c, e) Free energy diagram. (135)
Copyright 2020, Royal Society of Chemistry.
1.4.5. Applications Of MOF-Based/MOF-Derived Electrocatalysts For HER
1.4.5.1. HER Main Mechanisms
One essential semi-reaction for converting electrical energy into storable hydrogen is
electrochemical water reduction, or HER. HER is a method that produces hydrogen on
the cathode of water electrolysers (136, 137).
This two-electron transfer method works well in acidic or alkaline conditions for the
following chemical steps: (1st) The electrocatalyst adsorbs H2O or H species on the
cathode in the Volmer step. (2nd) The desorbed hydrogen on the cathode occurs via the
electrochemical or chemical Heyrovsky step or Tafel step.
(138) The Volmer-Heyrovsky mechanism and the Volmer-Tafel mechanism are the two
divisions of the HER reaction mechanism that follow the previously mentioned reaction
stages.
Adsorbed hydrogen (𝐻𝑎𝑑 ) is created when protons in the electrolyte mix with the electrons
on the electrode surface in an acidic environment. Had can then interact with other 𝐻𝑎𝑑 or
protons in the electrolyte to make hydrogen (H2).
35
The Volmer-Heyrovsky mechanism is the one that produces hydrogen when (𝐻𝑎𝑑 ) and
proton are combined, whereas the Volmer-Tafel mechanism produces hydrogen when had
and proton are combined (Fig. 11).
Under alkaline circumstances. Water dissociation is the initial step, after which the
Heyrovsky or Tafel pathway produces hydrogen (Fig. 11b).
(139) The Tafel slope, which is directly related to the HER process, is the size of potential
difference required when the current density increases or drops ten times. Because of this,
we may deduce the reaction's rate-determining step from the Tafel slope value, which
allows us to ascertain the reaction's mechanism.
The aforementioned reaction mechanism states that the production of intermediate H*

occurs in both the Volmer–Heyrovsky and Volmer–Tafel pathways. It is established that
the free energy of hydrogen adsorption (ΔGH*) controls the HER reaction rate. ΔGH* on
the catalyst surface should be about zero, with the ideal hydrogen adsorption energy being
neither too strong nor too weak. Additionally, the catalytic activity of the catalyst in an
acidic media is better than that in an alkaline medium under other equivalent conditions
because there is one more water dissociation process in an alkaline medium than in an
acidic medium. The energy needed for the adsorption of hydrated protons (H3O+) in the
Volmer stage of the HER under acidic conditions is significantly less than that needed to
break the H–O–H bond of the water molecule under alkaline settings, which explains why
the HER is more advantageous under acidic conditions (140, 141). created a HER rate-
volcano diagram in acidic circumstances and computed a range of H binding energies on
the various catalytic surfaces. (Fig. 11c). The volcano demonstrates a correlation between
the free binding energy and the hydrogen exchange current density on several transition-
metal surfaces. The correlation between practical observations and theoretical predictions
also clearly demonstrates how DFT catches the latent trend of HER electrocatalyst on the
transition-metal surface (Fig. 11c).
Significant understanding of the three fundamental HER steps—the Volmer, Heyrovsky,

and Tafel steps—is also gained, as illustrated in Figs. 11d–e. Specifically, it is learned that
the H binding energy is proportionate to the activation energy of H2 gas production. The
potential barrier of H2 production is higher if the binding energy of H is lower. Similarly,
36
a higher H binding energy results in a lower H2 production barrier, which may lead to
surface adsorbed hydrogen poisoning (142). Consequently, active centres' local
environment and coordination structure play a critical role in modifying their
performance.
Figure 11 Catalytic process mechanism diagram on the catalyst surface under acidic
(a) and alkaline (b) conditions. (144) Royal Society of Chemistry Copyright 2021. (c)
The connection between activity and H free binding energy. The curve is derived from
the microkinetic theory, and the circles represent the experimental results. The scaling
relationship between the activation barrier and H free binding energy in the Volmer and
Tafel stages (d) and (e).(142) Copyright 2018, WILEY-VCH.
1.4.5.2. MOF-Based HER Electrocatalysts
1.4.5.2.1. Noble Metal-Based Electrocatalysts.
The most active electrocatalysts for HER are still thought to be those based on noble
metals (143, 144). They are known to be costly, prone to aggregation, and unstable
throughout the HER procedure, though. Lately, a great deal of work has gone into
37
customising their performance, which has resulted in encouraging deliberate
advancements. Combining noble metals with MOF materials has allowed researchers to
accomplish remarkable results in recent years. This combination not only allowed for
good noble metal dispersion but also improved activity and reduced cost by modifying
atoms in the coordination environment. These accomplishments are necessary for mass
production of pure hydrogen. For instance, Rui et al. created 2D Ni-MOF@Pt and 2D Ni-
MOF@Pd noble metal/2D MOF heterostructures by incorporating highly scattered noble
metal NPs (such Pt and Pd) at oxygen sites on the MOF surface (Fig. 12Aa) (145). To
improve the electrochemical HER in both acidic and alkaline conditions, the 2D Ni-
MOF@Pt hybrid with modified electronic structure and well-defined interfaces was
investigated (Fig. 12Ab-c). Although it is still somewhat difficult, modifying the
interfacial bond interactions between the metal and support is thought to be a useful
method of maximising the catalytic performance of noble metals.
Many quantum-sized noble metal NPs anchored on Ni-MOFs (M@Ni-MOF, M = Ru, Ir,
Pd) have been logically constructed based on this idea. Ru NPs and Ni-MOF are joined
by metal-oxygen bonds, and Deng et al. rationally used a spontaneous redox process to
anchor quantum-sized Ru NPs on Ni-MOF (Ru@Ni-MOF) (Fig. 12Ba).
Ru@Ni-MOF had a Tafel slope of 40 mV dec-1 and an overpotential of only 22 mV when

the current density was 10 mA cm-2 in 1.0 M KOH. Sufficient exposure to the surface-
active areas and structural stability are guaranteed by the metal–oxygen linkages that bind
the NPs to the Ni-MOF. Furthermore, such a precise interfacial feature may effectively
alter the electronic structure of hybrids, improving the reaction kinetics by transferring
charges across the formed NiO-M bridge.
As a result, at all pH values, the representative Ru@Ni-MOF demonstrated excellent

HER performance. The enhanced HER performance of Ru@Ni-MOF can be explained
by the optimised adsorption free energies of hydrogen and water due to the interfacial-
bond-induced electron redistribution, as revealed by theoretical simulations (Fig. 12Bb-
c),(146).
38
By increasing the rate at which noble metal atoms are used, high HER electrocatalytic
activity can be achieved. Therefore, by interacting with one another, the noble metal
single atoms added to MOFs can modify the single atoms' local electronic structure.
Lately, an ion exchange approach has been used to synthesise Ru single atoms on Ni-
DBC (NiRu0.13-BDC), controlling the electronic structure of both Ru and Ni atoms (Fig.
12Ca). At all pH levels, the as-synthesised NiRu0.13-BDC demonstrated the strong
catalytic activity of HER (Fig. 12Cb). The overpotential and Tafel slope of the NiRu0.13-
BDC electrocatalyst were only 36 mV and 27 mV dec-1 at 10 mA cm-2, respectively,
which is equivalent to the performance of commercial Pt/C. This was especially true in 1
M PBS solution medium.
(Fig. 12Cc) shows specific charge accumulations around Ru and charge deficits near Ni.
It demonstrates that the electrical structure of the metal core may be modulated by adding
Ru. After doping Ru atoms, the Ni d-band centre moved to a lower energy, which
decreased the strength of the H* adsorption (Fig. 12Cd-e) (147).
39
Figure 12 A. (a) FT-EXAFS profiles of Ni-MOF@Pt. (b) Structure diagram at Ni-
MOF@Pt. (c) The curve for linear sweep voltammetry (LSV).(145) Copyright 2019,
American Chemical Society. B. (a) Ru@Ni-MOF structure diagram. The Ru@Ni-MOF
diagrams of (b) H2O adsorption energy and (c) ΔGH* diagram. (146) Copyright 2021,
Wiley-VCH. C. The electrical structure of the metal core is controlled by individual
noble metal atoms. (a) Diagram showing the NiRu0.13-BDC electrocatalyst preparation
procedure. (b) NiRu0.13-BDC's LSV curve in 1 M PBS. (c) The charge density
difference diagram. (d) Ni-BDC and NiRu0.13-BDC DOS calculations. (e) NiRu0.13-
BDC's computed free energy diagram of the HER (147) Copyright 2021, Nature
Publishing Group.
1.4.5.2.2. Transition Metal-Based Electrocatalysts.
Many unpaired d-orbital electrons can be found in transition metal atoms, including Fe,
Co, Ni, and Cu, etc. (148-150). Consequently, the material's hydrogen evolution
efficiency can be increased by employing the transition metal as the MOF electrocatalyst's
active centre, which can also give the material a strong hydrogen absorption capacity.
Hexaiminohexaazatrinaphthalene (HAHATN) was used as a conjugated ligand by Huang
et al. to create bimetallic sited conductive MOFs (Ni3(Ni3⋅HAHATN)2) with an extra Ni-
N2 moiety (Fig. 13Aa-b). The η10 and Tafel slope of HAHATN were 51 mV and 45.6
40
mV dec-1, respectively. The material's propensity to give off electrons was strengthened
since the Ni-N2 portion was more unsaturated than the Ni-N4 portion. Furthermore, a
DFT calculation revealed that Ni-N2 has a greater capacity for adsorption than
intermediates. (Fig. 13Ac). (148).
Additionally, transition metals worked in concert to improve electrocatalytic activity.

According to Geng and colleagues, conductive Cu-catecholate (CuCAT) nanorods were
produced directly on flexible carbon cloth after Co atoms were added (Fig. 13Ba).
Electrochemical experiments demonstrated that in an alkaline medium, the CoCu-based
bimetallic organic framework can generate a current density of 10 mA cm-2 with a low 52
mV overpotential and a 51.8 mV dec-1 Tafel slope (Fig. 13Bb). This was explained by the
fact that the Co atom's introduction can work in concert with the Cu site to maximise the
material's active site's ΔGH* and ΔG H2O (Fig. 13Bc) (150).
The Cu-Ox activity was recently investigated by Lou's group from the standpoint of
atomic coordination. Fe(OH)x@Cu-MOF nano boxes' strong hollow nanostructure and
highly exposed electrocatalytic active centre significantly increased the catalyst's
exceptional activity (overpotential of 112 mV and Tafel slope of 76 mV dec-1) and
stability (Fig. 13Ca). With unsaturated coordination, the Cu nodes are distributed
throughout a planar Cu1-Ox structure (Fig. 13Cb). The saturated and unsaturated
coordination centres of Cu nodes are represented by Cu-O4 and Cu-O2, respectively. The
LSV curve of (Fig. 13Cc) indicated that Fe(OH)x@Cu-MOF exhibited HER activity in
proximity to Pt/C. From a thermodynamics standpoint, the Cu1-O2 centre’s local
polarisation promoted its strong adsorption with H2O, which sped up the process of water
splitting. (Fig. 13Cd).(149). Generally speaking, the highly exposed and unsaturated
coordinated Cu1-O2 centre speeds up the generation of H* intermediates and supports the
HER process, which is essential for enhancing electrocatalyst performance (149). These
findings suggested that various coordination topologies have a significant impact on the
catalytic process.
41
Figure 13 A. (a) The structure diagram and (b) the HER polarisation curve of
Ni3(Ni3•HAHATN)2 MOFs. (c) Curves of free energy .(148) Copyright 2020, WILEY-
VCH. B. (a) CuCo-CAT structure schematic diagram. (b) An excess of 100 mA cm− 2
overpotential. (c) ΔGH* determined using DFT. (d) the H2O adsorption energy on the
materials' surface for HER. (150) Copyright 2020, WILEY-VCH. C. (a) The Cu-MOF
structural diagram. (b) Cu K-edge EXAFS spectra Fourier transform curves for
Fe(OH)x@Cu-MOF NBs. (c) The LSV curve. (d) Cu1-O4 and Cu1-O2 centres' variation
curve for the free energy of H* adsorbed at Cu sites.(149) Copyright 2021, American
Association for the Advancement of Science.
We can infer from the aforementioned uses of MOF-based electrocatalysts that MOF's
ability to precisely control and alter its metal nodes and organic ligands to optimise
electrocatalytic activity makes it an effective electrocatalyst.
Both noble metal-based (Pt, Ru, etc.) and transition metal-based (Co, Fe, Ni, etc.) MOF
electrocatalysts continue to exhibit significant levels of electrocatalytic activity. The
comparatively low conductivity of MOF-based HER electrocatalyst is, however, its
42
greatest drawback. Consequently, a few tactics can be employed to maximise MOF-based
electrocatalysts' electrocatalytic activity. Combining MOF materials with functional or
carry materials, for instance, will result in synergistic effects that influence their catalytic
activity.
Additionally, transition metals and aromatic organic ligands were used to create
conductive MOF materials. Its π-π conjugate structure helps to increase the
electrocatalysts' ability to transport electrons. Furthermore, increasing the electrocatalytic
activity can be achieved by making better use of the active centre atoms. (Table 4)
provides an overview of the performance of newly reported MOF-based catalysts for
electrocatalytic HER.
Overpotent
ial
Material Tafel slope
Electrocatalysts Substrate Electrolyte (mV) at
types (mV dec-1 )
10 mA cm-
2
NiRu13-BDC NF 1M PBS 36 32
GCE 0.5 M H₂SO4 43 30

2D Ni-MOF@Pt
NSs
GCE 1M KOH 102 88
NF 0.5 M H₂SO4 29 55.7
Noble Ru-NiFeP/NF NF 0.1 M PBS 105 82.7

metal –
based NF 1.0 M KOH 56 67.8
electrocata
lyst GCE 0,1 M KOH 66 101.6
Pt/ MOF-O
GCE 0.5 M H₂SO4 28 24.4
NF 1.0 M KOH 22 40
Ru@Ni-MOF NF 1.0 MPBS 287 62
NF 0.5 M H₂SO4 112 33
43
Fe3S4/MIL-53 GCE 0.1 M H₂SO4 92 60
FePc@NI-MOF GCE 0.1 M KOH 334 72.1
Fe(OH)x@Cu-MOF CP 1.0 M KOH 112 76
pH 1.3
FeBHT GCE 173 119
H₂SO4
2D Co-BDC /Mo GCE 1M KOH 248 86
0.05 M
CoTHT GCE 143 70.6
H₂SO4
Transition pH 1.3
CoBHT GCE 185 88
metal - H₂SO4
based
CC 1M PBS 49 63
electrocata
CoP/Co-MOF CC 1 М КОН 34 56
lyst
CC 0.5 M H₂SO4 27 43
WE 0.5 M H₂SO4 52 49
(2D)CoP/Co -MOF WE 1.0 MPBS 106 89
WE 1.0 M KOH 26 53
Gr and Co-MOF GCE 0.5 M H₂SO₂ 125 91
NiCo-MOF/rGOAS GCE 0.1 M KOH 210 73
pH 1.3
NiBHT GCE 331 67
H₂SO4
Table 4 HER performances of MOF-based electrocatalysts (GCE: glassy carbon

electrode; CC: carbon cloth; CFP: carbon Fiber paper; FTO: fluorine-doped tin oxide;
NF: Ni foam). (137)
44
1.4.5.2.3. Examples Of the Most Active HER- MOFs Electrocatalysts
Table (6) shows examples of HER electrocatalysts MOFs with their characterization
results and electrochemical measurements that were performed with supportive
comparison that clarified in the (Fig14,15).
Figure 14 Overpotentials of the Overpotentials of the reported HER

active MOF electrocatalysts for
electrocatalysts with reported HER comparison at 10 mA·cm−2 in 0.5
activity in MOFs. M H2SO4 electrolyte
300
LSV mV at a current density of 10 mA cm−2

230
193
200
124
100 76
47
0
MoOx/Ni3S2/NF
1
Ni (OH)2/CoNi2S4/NF
catalyst
Co, P- /Codopd MoS2 /Nano Flowers
The new flower-like 2D/3D MOF {[Co (BIPA)(5-

OH-bdc)] (DMF)} n
Iridium on vertical graphene
Figure 15 Tafel slope of the MOF Tafel slope of the reported HER
active MOF electrocatalysts for
electrocatalysts claimed to be active by comparison in 0.5 M H2SO4
HER. electrolyte
100
84
77.1
Tafel slope mv dec-1
53
46 43
50
0
MoOx/Ni3S2/NF 1
Ni (OH)2/CoNi2S4/NF catalyst
Co, P- /Codopd MoS2 /Nano Flowers
The new flower-like 2D/3D MOF {[Co

(BIPA)(5-OH-bdc)] (DMF)} n
Iridium on vertical graphene
45
Basic Table for HER active MOFs (Table 5).
Assessm
ent of
electroc
Physical characterization Electrochemical analyses
atalytic
HER
activity
Electroche
Synthesis
mical MOF
Method of
catalyst / SAED
MOF
testing pattern /
catalyst.
condition scannin EDS
g mapping /
electron TEM powder X- Tafel TOF
LSV EIS Cdl HER stability
Ref
microsc image ray slope number
opy diffraction
(SEM) (XRD) /
Raman
spectra
42mF∙cm2
extremely
small Rct
MoOx/ MoOx/ This large
of 6.51 Ω
Ni3S2- Ni3S2 Cdl unveils
MoOx/Ni3
11The spheres the large
S2/NF-11
special are amount of
has faster
skeleton compris electrochem
the SAED charge
of NF ed of ical active
pattern transfer
provide nanopar sites in the
which dynamics
s large ticles. MoOx/Ni3S
displays in HER
surface 2/NF-11.
characterist process.
MoOx/Ni3 area and These
The ic crystal
S2/NF one-pot ideal the η10 results
(151-155)
lattices planes of 46mV∙de
solvotherm mechan of 76 The fast reveal that
of 0.24 Ni3S2 and c‒1
al reaction ical mV charge the
0.5 mol∙L‒ and diffuse
stability transfer is MoOx/Ni3S
1 H2 SO4 0.29 nm rings of the
. probably 2/NF-11
are amorphous
MoOx. attributed with oxygen
ascribed
to vacancies
irregula to (003)
synergetic generates
r small and ____________ ______
effect of more
spheres (110) _ __-
the accessible
grown crystal
amorphous active sites,
on the planes
MoOx and thereby
substrat of
the Ni3S2 promoting
e Ni3S2
nanoparticl the H2
es evolution
process.
46
exhibits
nanoflo
wers
structur
e
compos
ed of
nanowir
large e arrays
number and
it can be found
of Ni nanoshe exhibits a
only 84 that Ni
(OH)2/ ets, in only 124 Cdl value of
mV (OH)2/CoNi2
NiS agreem mV at a 27 mF cm-2
dec−1, S4/Displays
nanoshe ent with current . It can be The higher
indicatin negligible
ets were the density seen that the Cdl
g that degradation
verticall results of 10 Ni value of Ni
Ni synthesize the aftern2000CV
y grown of its mA (OH)2/Co (OH)2/CoNi
(OH)2/Co d by HER. cycles. chrono
on the SEM cm−2 Ni2S4/NF 2S4/NF
Ni2S4/NF simple potentiometric
surface image indicatin exhibits the indicates its
hydrother curve at a
lattice g that smallest larger
(156-161)
mal of process controlled
nickel fringes the semicircle, ECSA,
reaction undergo current density
foam. with introduc demonstrati which is
and es of 10 mA cm−
distance tion of ng its beneficial to
subsequent Volmer- 2 for 30 h. Ni
0.5 M H2 s of Co can lowest Rct exposing
sulfurizati nanoflo Heyrovs (OH)2/CoNi2
SO4 0.233 improve value at the more
on wers ky S4/NF shows a
and the electrode/el catalytic
compos mechani stable
0.283 _________ catalytic ectrolyte active sites ______
ed of sm. potential
nm __ activity interface and improve ___
nanowir response for
corresp of the the catalytic
e arrays HER without
ond to material. activity of
and significant
(101) the material.
nanoshe degradation
plane of
ets. Ni
(OH)2
(PDF#1
4–0117)
and
(311)
plane of
CoNi2S
4
47
nanoflo
wer-like
structur
e
consisti
ng of
ultrathi
n
nanoshe
Flower ets,
like which
shape, is 230 mV
consisti consiste to drive
ng of nt with the
2D the current
ultrathi SEM density
n results. of 10
nanoshe MoS2 mA The
ets of is a cm−2 maximum
the layered Cdl value,
sample, structur has the in
e, which smallest particular, is
which means charge- calculated to
nanoflo is EDS that Co, the transfer be 37.05.
wer- compos mapping P-MoS2 smallest resistance
shaped ed of further requires polarization
Tafel (89.9 Ω)
nanoflowe Co, P- several reveals Co the least mF cm−2 curve does not
slope
r-like MoS2 layers, and P amount for Co, P- change much,
(about
Co, P‑ MoS2with material indicati elements of MoS2
53 mV
Codopd the porous s are ng that successfull energy dec−1
MoS2 structure compos the y doped to
Nano containing ed of prepare intoMoS2 generate which above result
Flowers defects by tens to d nd H2 indicates reveals that
and the current
(162-165)
doping hundred sample indicates under that Co, P- MoS2 with
density is still
with Co s of has an that the Co, the same MoS2 Co and P
very large
and P MoS2 ultrathi P, Mo, and conditio which composite codoping
after 1000
atoms with nanoshe n S atoms ns (low indicates possesses possesses
cycles of CV,
the ets, and layered were energy that it better the highest
0.5 M H2 suggesting that
hydrother the size structur evenly barrier), possesse charge- value of
SO4 Co, P-MoS2
mal of e. the distributed demonst s the transfer ECSA,
have relatively
method nanoflo distance throughout rating strongest properties which can
good HER
wers is between the that Co electroch and a faster effectively
stability.
about the nanomateri and P emical Faradaic improve
800 nm. layers, als synergis kinetics process in electrocatal
A large the tic HER ytic activity
number layer doping kinetics for HER in
than other a rational _______-
of fold spacing indeed
structur of the plays a adsorption/d
es can synthesi crucial esorption
be zed Co, role in process
observe P-MoS2 enhanci
d, and can be ng the
these measure electroc
folds d as atalytic
expose 0.73 activity
more and of MoS2
active 0.27
sites... nm,
which
corresp
onds to
the
(002)
and
(100)
surfaces
.
48
electron
because of the
diffraction
alternate
SAED, and
The Co accumulation
powder X-
nanopar and release
ray
ticle processes of
diffraction
and the H2 (g) bubbles
(XRD) The
constructe graphiti the current
peak at
d based on c density is
exhibits about 26.2_
bis(4-(1H- carbon stable without
flower- correspond
imidazol- show degradation
like s to the
The new 1-yl) clear even after
morpho (002)
flower-like phenyl) lattice long-term
logy. diffractions
2D/3D amine spacing cycling for 20
the of graphitic The
MOF [[Co (BIPA) of 0.205 h.
resultan carbon, and overpote
(BIPA)(5- and 5- nm and
t Co, N- the peaks at ntials to
OH-bdc)] hydroxyiso 0.337 lower
doped about 44_, achieve
(DMF)](54 phthalic nm Tafel
carbon 51_, and the
)n acid (5- corresp slope
Co- 71_ are current
OHH2bdc) onding (77.1
MOF- attributed density the
(166-171)
to mV
800 to metallic of 10 polarization
decade_
keep the Co. Raman mA curves for the
After that, 1) for
flower- the Co spectra cm_2 Co-MOF-800
the CoeN- the Co-
like (111) reveal the for the electrode
doped MOF-
morpho and characterist Co- before and
carbon 800.
logy carbon ic (~1587 MOF- after the
0.5 M H2 composite
well (002) cm_1) and 800 193 _________ __________ continuous
SO4 along planes D (~1349 mV. HER process ________
_____ ____
Co-MOF- with respecti cm_1) (20 h),
800 was porous vely bands of showing only
prepared feature carbon, a slight
via of the which are deactivation.
calcination petals. related to
of MOF 1. graphitic
sp2-carbon of the activity
and on the Co-
disordered/ MOF-800
defective electrode.
carbon,
respectivel
y.
the VG
nano
hills
with an
average
Iridium on VG is height
vertical clearly of _40
graphene visible nm. The
with its magnifi
disperse distincti ed
crystalline ve image
Ir layers nano- validate low
with hill-like s the overpote TOF
various structur crystalli ntial 47 In acidic
values
thicknesse e after ne mV was media,
reached 1.7
s (1–10 the nature observe Ir_VG
s_1 and 4.1
nm) depositi of d in showed For the HER, s_1 at
(172-176)
on of Ir Ir.The 0.5M H2 HER Ir_VG showed overpotenti
by e- observe SO4, Tafel almost no loss
uniformly als of 100
beam d lattice slope after 1000
on the _________ _________ __________ mV and
evapora fringes value of cycles in
0.5 M H2 forest-like __ ___ ___ 200 mV,
tion, the (parallel 43 mV acidic Solution
SO4 VG by the respectivel
edges of lines) dec_1
e-beam y.
VG with a
evaporatio become distance
n more of 0.22
technique. promine nm can
nt. be
attribute
d to the
well-
defined
Ir (111)
facet of
the fcc
lattice.
Table 5 Basic Table for HER active MOFs
49
2. Experimental Method
2.1. Materials.
Cobalt- nitrate Hexahydrate (Co (NO3)2·6 H2O), Iron nitrate nano hydrate (Fe (NO3)3·9
H2O), Benzimidazole as an organic linker, Triethylamine,0.5M sulfuric acid (H2SO4),
Dimethylformamide (DMF), methanol, ultrapure water (Fig 16).
Centrifugation device to separate the mixture, vacuum drying to dry the resultant powder,
autoclave for the reaction mixture, furnace at high temperature for catalyst preparation,
CVD device for calcination MOFs catalyst, porcelain boat, Ag/AgCl electrode as a
reference electrode, Glassy carbon electrode as working electrode to be coated with the
MOF ink, pt wire as a counter electrode, Nitrogen gas to be used through the calcination
process and the electrochemical measurements.
40% Platinum on Vulcan powder, ethanol (EtOH), sonication device for mixing the ink
samples, Nation (20wt%) and carbon black were used for ink preparation.
Figure 16 Initial chemicals for MOFs synthesis
2.2. Synthesising Different Types of Transition Metals-Based MOF As HER

Electrocatalyst
2.2.1. Synthesis Of Mono-MOF With Solvothermal Preparation Methods
At the early-stage Mono (Co or Fe)-MOFs was synthesized at lab scale by using
solvothermal synthesis methods (Fig 17)(Fig 18), by adding one kind of metal salt
(0.7165 g /2.4618× 10−3 mole of Cobalt nitrite hexahydrate or 0.374 g/0.92486 × 10−3
mole of Iron nitrite monohydrate) to organic linker (2.333 g/19.74× 10−3 mole of
50
benzimidazole), and using 50ml mixture of solvent (20 ml of DMF,15 ml of ethanol and
15 ml of water) for each of the metals and 50 ml of mixture of solvent for the linker to
ensure the solubility of the reactants, Finally 0.5ml of triethylamine was added to
accelerate deprotonation of the organic linker ,with continuous stirring of the mixture for
one hour, then transfer the mixture of reactants into autoclave. Reaction within the
autoclave tool requires to put the autoclave sample at high pressure and temperature about
180 c in furnace for 24h. after one day reaction was completed, the autoclave sample was
taken out of the furnace and cooled naturally at the room temperature until the next day,
then the resultant mixture was washed three times with methanol and then with water and
centrifuged and dried at 40◦C in drying vacuum.
Figure 17 powder of prepared Co-MOF electrocatalyst
Figure 18 powder of prepared Fe-MOF electrocatalyst
2.2.1.1. Calcination Process for Co-Based MOF
Calcination process was conducted by utilizing CVD technique, the prepared

nanocrystals CO-based MOFs (0.1g) was placed into a porcelain boat, in the middle of
quartz tube in CVD device under the nitrogen gas flow the boat was put, before start
51
heating, purging of the quartz tube with nitrogen gas for 20 min has been done to drain
the air inside. After that, heat supply has been initiated gradually from room temperature
until the aimed temperature (900) under continuous Nitrogen gas for 5 h. Finally, the
furnace was naturally cooled to room temperature to obtain carbon -coated core shell
structure of nanocomposite materials or cobalt calcinated MOF (Fig. 19)
Figure 19 Co-MOFs after calcination by CVD device.
2.2.1.2. Calcination And Metal Loading Process for Co-Based MOF
calcinating and metal loading step of the prepared nanocrystals CO-based MOFs was
done in Similar procedures like the previous calcination process, for this step mixture of
CO.MOF, Cobalt nitrite hexahydrate, and Iron nitrite monohydrate with the same weight
ratio has been grounded until getting homogeneous before transferring it into porcelain
boat.
2.2.2. Synthesis Of Bimetallic -MOF With Different Preparation Methods
2.2.2.1. Synthesis Of Co.Fe. MOFs With Preparation Method(A)
The main changes that were made with method A will be represented by heating
temperature and time to see their effects on the efficiency of the catalyst. Bimetallic (Co.
Fe.MOF) Transition metal -based MOFs were prepared by adding two kind of metal salts
(0.358 g /1.23× 10−3 mole of Cobalt nitrite hexahydrate and 0.358 g /1.23× 10−3 mole
of Iron nitrite monohydrate) to organic linker (2.333 g /19.74× 10−3 mole) of
benzimidazole),with molar ratio of metal: ligand 1:8 ,and using 50 ml mixture of solvent
(20 ml of DMF,15 ml of ethanol and 15 ml of water) for each of the metals and 50 ml of
52
mixture of solvent for the linker to ensure the solubility of the reactants, with continuous
stirring and heating temperature about 85C of the mixture for one hour, with adding 0.5ml
of TEA triethylamine to accelerate deprotonation of the organic linker. Then the mixture
was cooled naturally at the room temperature, then the resultant mixture was washed three
times with methanol and then with water and centrifuged and dried at 40◦C in drying
vacuum.
2.2.2.1.1. Calcination And Metal Loading Process for Bimetallic Co.Fe. MOFs
Calcinating and metal loading of the obtained nanocrystals Co.Fe.MOF has been done
again in Similar procedures like the previous calcination process, however new and more
advanced CVD device was utilized for this process with different parameters include
heating temperature up to 1000c for 2h, mixture of Co.Fe.MOF, Cobalt nitrite
hexahydrate, and Iron nitrite monohydrate with the same weight ratio was grounded until
getting homogeneous before transferring it into quartz boat, finally Co.Fe.C.MOF/Fe. Co
has been obtained.
2.2.2.2. Synthesis Of Co.Fe. MOFs With Preparation Method(B)
The main target for this case study is to show the effects of changing the amount of metal
and the ligand with changing the molar ratio of metal: ligand 1:2, the type of solvent
beside the heating temperature and duration. Bimetallic (Co/Fe -MOF) Transition metal
-based MOFs were prepared by adding two kind of metal salts ( 0.7153 g of Cobalt nitrite
hexahydrate and 0.7153 g//2.4618× 10−3 mole of Iron nitrite monohydrate) to organic
linker (1.165 gr /9.8738 × 10−3 mole of benzimidazole), and using 50 ml DMF solvent
for metal salts and 50 ml of the same solvent for the linker to ensure the solubility of the
reactants with continuous stirring and heating temperature about 85C of the mixture for
one hour, with adding 0.5ml of TEA triethylamine to accelerate deprotonation of the
organic linker. Then the mixture was cooled naturally at the room temperature, then the
resultant mixture was washed three times with DMF and then with water and centrifuged
and dried at 40◦C in drying vacuum.
53
2.2.2.2.1. Calcination And Metal Loading Process for Bimetallic Co.Fe. MOFs
(B)
Calcinating and metal loading step of the nanocrystals Co.Fe.MOF was done again in
Similar procedures like the previous calcination process (Co-MOF), for this stage mixture
of Co.Fe.MOF, Cobalt nitrite hexahydrate, and Iron nitrite monohydrate with the same
weight ratio was grounded until getting homogeneous before transferring it into porcelain
boat, finally Co.Fe.C.MOF/Fe. Co has been obtained.
2.3. Preparation of MOFs Ink Composite
5mg of prepared MOF (mono or bimetallic) was mixed with 3mg of carbon black, 10 µl
of Nafion solution (20wt%), 45 µl of water, and 135 µl of ethanol, then this step was
followed by sonication for 1 hour until obtain a uniformly dispersed suspension, then
glassy carbon electrode was coated with a specific amount of the prepared suspension
(20µl) by using micro syringe, finally, dried in Nitrogen atmosphere at room temperature,
leading to an appropriate catalyst loading.
Pt ink was prepared for comparing MOF samples performance in similar way with
replacing 5mg of MOF catalyst powder with 5mg of Platinum on Vulcan powder (Fig
20).
Figure 20 ink of different MOF types
54
2.4. Catalyst Characterization Techniques:
At the second stage, molecular level analysis for the synthesized MOFs were performed
by two types of fundamental characterization techniques which are X-ray diffraction
(XRD) and 3 Fourier transform infrared (FT-IR).
2.4.1. FTIR Spectroscopic Studies
the chemical structure and functional groups of the as-synthesized catalysts were recorded
via Shimadzu IR Prestige 21 model Diamond by ATR method.
2.4.2. XRD Measurements
identification of the crystalline structure of as synthesized MOFs samples was conducted

by the X-ray diffraction (Bruker D2 Phaser X-ray diffractometer under Cu Kα irradiation
at 10°<2𝜃<90°).
2.5. Electrochemical Measurements
Conventional three- electrode cell was used for all electrochemical measurements,
besides Gamry Instruments Reference 600 as a potentiostat/galvanostat/ZRA. The Glassy
carbon electrode loaded with catalyst inks was used as the working electrodes with
electrode area (0.071cm2), and a Pt wire and Ag/AgCl electrode were used as counter
and reference electrodes, respectively. All the experiments were carried out at 25 ± 1, 0.5
M H2SO4 was used as an electrolyte with PH value (-0.30), within Nitrogen atmosphere.
All the polarization curves were recorded using linear sweep voltammetry (LSV). Linear
sweep voltammetry (LSV) was used as the first beneficial tool for analyzing MOFs
catalyst activity and assessing the electrochemical reactions at the cathodic area, with a
scan rate 5 mV s-1, initial E(V) was recorded as (0.2V), and final E(V) was recorded as
(-0.35 V).
All the obtained potentials in this work were converted to reversible hydrogen electrode
(RHE) by the Nernst Equation
°
𝐸(𝑅𝐻𝐸) = 𝐸𝐴𝑔/𝐶𝑙 + 0.059𝑃𝐻 + 𝐸𝐴𝑔/𝐶𝑙
55
°
Where 𝐸𝐴𝑔/𝐶𝑙 is the obtained values of working potential from LSV curve, and 𝐸𝐴𝑔/𝐶𝑙 =
0.1976 Vat 25° C and this value will be added to -0.0177 (=-0.30×0.059) to obtain 0.1799
and finally added to 𝐸𝐴𝑔/𝐶𝑙 to complete the conversion to standard reversible hydrogen
electrode.
The overpotential (𝜂) was calculated using the following equation:
𝜂(𝑉) = 𝐸𝑅𝐻𝐸 − 0𝑉 for HER
The polarization curves were replotted again as an overpotential (η) versus log current
(log J) to get Tafel plots, and then linear portion from the plot was fitted to the Tafel
equation to obtain Tafel slop value which represent the second versatile tool to assess
HER kinetics and rate determining step. Tafel slop was modulated by Tafel equation.
𝜂 = b log 𝑗 + 𝛼
Where 𝜂 is the overpotential, 𝑗 is the current density, b is the Tafel slop and 𝛼 is a
constant.
The interface reactions between electrolyte and electrode were characterized by running
the EIS experiment, and EIS is considered also as powerful technique to be used in
analysing the electrochemical process, The electrochemical impedance spectroscopy
(EIS) measurements were also taken from high frequency region to low frequency region
100000 Hz as an initial frequency to 0.1 Hz as a final frequency, in addition the value of
the used AC voltage was 10 mV/MS. Then the EIS measurements of as each type of as
prepared catalyst sample at different potential points were recorded in order to the see the
effect of increasing the overpotential on the charge transfer resistance , as well the same
EIS measurements for .MOFs sample and Pt catalyst, and GCE electrode were measured
for compering at a static potential of – 0.25 V to further demonstrate the following
parameters charge transfer resistance 𝑅𝑐𝑡 , solution resistance 𝑅𝑆 and the coating
capacitance 𝐶𝑐 respectively , the obtained EIS Nyquist plot, which displays the imaginary
part of impedance against the real part can be represented as semicircles, then Nyquist
curve was fitted to the simplex method model (REAP2CPE),then the important
parameters’ numerical values were extracted.
56
HER stability of the synthesized electrocatalyst through the hydrogen production by
water electrolysis technique is the fourth significant parameter that was recorded while
electrochemical assessment. to guarantee the catalytic stability though the hydrogen
production. MOFs stability at the cathodic area was checked out by running LSV
polarization curve for 100 cycles with a scan rate 5 mV s-1, initial E(V) was recorded as
(0.2V), and final E(V) was recorded as (-0.35 V). where there was no change between the
first cycle and the last cycle, suggesting high stable catalyst structure.
3. RESULTS AND DISCUSSIONS:
3.1. Synthesis Of Monometallic -MOF with Different Preparation Methods
3.1.1. Synthesized Co-MOF Electrocatalyst Type with Solvothermal Methods
3.1.1.1. Structural Characterization of Co.MOF Electrocatalyst:
3.1.1.1.1. Fourier Transform Infrared (FT-IR) Of Co.MOF Electrocatalyst:
The FTIR spectra of BIM and Co.MOF is displayed in the (fig 21). Starting from BIM
as a reference we can compare the differences with as prepared nanocomposite sample.
obviously, spectrum of BIM possesses the vibrations at around 2997,2557, and 2159 cm-
1
for N–H, and C–H respectively. Huang et al. (177) reported that benzimidazole organic
linker shows the aromatic C–H stretching vibrations between 3100 and 3000 cm−1 and
the stretch band of N–H group which absorbs strongly at 3250– 2500 cm-1 .
The most prominent change observed in FTIR spectrum of the Co.MOF sample is
represented in the disappearance the characteristic peaks at 2997,2557, and 2159 cm-1,
which are related directly to strong and broad bands N–H, and C–H and this can be a good
indicator that the ligand was fully protonated during the formation of Co.MOF structure,
which is assigned to the interaction of Co+2 with nitrogen in the linker (177). And as we
can see the appearance of characteristic Co–N stretching band between 3050-3200cm-1in
Co.MOF spectrum can support this point and indicate to the interaction between nitrogen
and benzimidazole (177). and the peak at 1977 became more broader and less intense
than BIM sample and almost disappear, as well the peaks at 1771 and 1587 cm-1 position
was shifted to 1774 and 1599 cm-1 and became more sharper and bigger than BIM case.
57
Add to that peak at 1477,1457,1400 were changed to be just one broader and longer peak
at 1454 cm-1, so all of the changing between 1600-1200cm-1 might be correlated with
changing in C-N and C=C within BIM structure after binding within MOF catalyst (177).
More precisely the Peaks between the range 1500-1400 cm-1 and 1400-1300 cm-1 might
correspond to aromatic C-C and C-N stretching vibrations, respectively.
Noticeably, there is disappearing in 418 peak and appearing new characteristic bands at
466,455,434,422 when Co.MOF. 543,643 BIM peaks became sharper and elongated and
changed in its positions to 550,647 indicating that new interactions were introduced when
the MOF new structure formed.
Figure 21 FTIR spectra of Co.MOF sample
58
3.1.1.1.2. X-Ray Diffraction (XRD) Of Co.MOF Electrocatalyst:
The crystalline structures of the as-prepared BIM, Co.MOF and Fe.MOF respectively,
were inspected by X-ray diffraction (XRD). As it exhibited in (Fig 22) where the
diffraction peaks are obviously and sharply appeared to indicate on the growth of well-
crystallized MOFs structure.as it was clarified in this figure the diffraction pattern was
altered due to coordination of metal ions (Co.Fe) into BIM ligand structure, causing the
positions and the intensities of the peaks to be changed ,more precisely the intensity of
both cases peaks was decreased indicating to formation of hybrid structure (178).
the characteristic diffraction peaks in The XRD pattern of the as-prepared Co.MOF
sample (blue line) were showed at 2θ of 11.56,12.56, 15.35,20.19, 21.76,23.34,
27.94,31.5,34.20,36.03,38.01,84.01, proving that cobalt based catalyst was crystallized
perfectly, corresponding to specific case study (179), add to that the shape of the obtained
peaks is coincide with the XRD pattern of the bulk Co2BIM4 as well as the simulated
pattern of M2(BIM)4 which also corresponding to this case study (180).
Figure 22 XRD pattern of BIM, Co-MOF, and Fe-MOF samples
59
3.1.1.2. Electrochemical Measurements
3.1.1.2.1. Linear Sweep Voltammetry Analysis for Co.MOF Electrocatalyst

Type:
Investigation the electrocatalytic HER effectiveness of Co.MOF was done by using

Linear sweep voltammetry technique to provide information about the electrochemical
process, three electrode cell system with nitrogen saturated environment at 𝟐𝟓° 𝑪, LSV
measurements with a scan rate of 5 mV s-1 were recorded for three cases, as prepared
electrocatalyst, commercial 40 wt. % pt catalyst coated on GCE as a reference, and bare
glassy carbon electrode without catalyst coating, respectively.
As the polarization curves displayed in the (Fig 23), the most perfect electrochemical
behaviour was possessed by Pt catalyst with η10 = 42 mv overpotential when current
density reached 10 mA.𝒄𝒎−𝟐 . Obviously, at the same cathode current extraordinary HER
performance was achieved by our synthesized cobalt-based MOF, the applied voltage was
too law and the current density increased sharply to obtain η10= 50mv overpotential, this
value approximately approaches the pt catalyst value and lower than glassy carbon
electrode overpotential which is about η10 = 560 mV, indicating to high efficiency
electrocatalyst and its capability to minimize the overpotential voltage, clearly this
considers one of the lowest overpotential between the previously reported HER catalyst
(table 6), summarize HER performance of the recently reported transition metal based
MOF and Nobel metal based MOF in 0.5 M H2SO4 and show compering with another
study that was done on Iridium on vertical graphene where low overpotential 47 mV at
current density 10 mA.𝒄𝒎−𝟐 was observed in 0.5 M H2SO4 and HER Tafel slope value
of 43 mV dec-1 (172). Additionally, these will provide great evidence about the powerful
of MOF catalyst structure that was prepared with one type of metal ion and exceed in its
performance the other prepared electrocatalyst such as bimetallic, trimetallic and the
heteroatoms loaded structure of MOFs, that required a lot of heating chemical processes.
if we compare this case with (2D) CoP/Co-MOF study in similar electrolyte which
represent transition metal based electrocatalyst with η10 =52mv overpotential and HER
Tafel slope value of 49mV dec-1 (191).
60
The remarkable electrocatalytic accomplishment might be attributed to the synergic
assistance to the coming factors: A) Introduce cobalt metal ions to the catalyst structure
plays a significant role to enhance the hydrogen adsorption energy which in turn lead to
accelerate HER Volmer step this behaviour is ascribed to cobalt high transition state
between 𝐶𝑜 +2 , and 𝐶𝑜 +1 during the adsorption /desorption process, as well this kind of
transition metal-based catalyst with unoccupied d-orbitals metal active centres (hydrogen
acceptor sites) could dramatically increase the HER performance (181). B) Solvent
exchange and removal procedure followed by thermal activation; this was an efficient
strategy to ensure MOF catalyst network retention by replacing the less volatile solvent
with more volatile solvent then washing MOF with water to remove it, and finally apply
thermal activation by vacuum drying , consequently generating more open metal site
(unsaturated centres) within MOF structure (182), as well as increasing the volume of
available micropores and the surface area ,and more interaction between hydrogen and
open metal ions. C) Imidazolate ligand structure contribute also to increase catalyst
functionality with tow pair of the electrons located at nitrogen atoms that can contribute
to hydrogen bonding, beside the existence of the aromatic group that can maximize the
utilization of the atoms and gives full play to the metal centres by increasing their
exposure. D) The high porosity generated by using benzimidazole provides high surface
area electrocatalyst with high efficiency (183).
Figure 23 polarization curve commercial pt, Co.MOF, GCE electrode
61
Overpotential
Tafel slope (mV
Electrocatalysts Electrolyte (mV) at 10 mA Ref.
dec-1)
cm-2
Co.MOF 0.5 M H2SO4 50 38.57 This work
CoBHT 0.5 M H2SO4 185 88 (184)
Iridium on
vertical 0.5 M H2SO4 47 43 (172)
graphene
(2D) CoP/Co-
0.5 M H2SO4 52 49 (185)
MOF
Gr and Co-
0.5 M H2SO4 125 91 (186)
MOF
2D Co-
0.5 M H2SO4 143 70.6 (187)
BDC/MoS2
Table 6 summary of HER performance of the previously reported MOF catalyst
3.1.1.2.2. Tafel Slope Analysis for Co.MOF Electrocatalyst Type:
The catalytic mechanism of the synthesized Co.MOF was investigated by employing

another advantageous analytical tool which is defined as Tafel slope.in order to obtain
Tafel plot, the polarization curve was replotted against the logarithm of the current
density, then fitting linear portion of the Tafel plot into the Tafel equation, as (Fig 24)
displays that Tafel slope was obtained as a numerical value. For comparison the slope
was calculated for cobalt catalyst, Pt catalyst, and for glassy carbon electrode
respectively. The obtained numerical values were 38.57 𝒎𝑽. 𝒅𝒆𝒄−𝟏 for Co.MOF, this can
generate another proof about high HER performance with high kinetic electrochemical
reactions which follow the Volmer-Tafel mechanism, which similar to Pt catalyst
mechanistic pathway with numerical value is about 34.32 𝒎𝑽. 𝒅𝒆𝒄−𝟏 . indicating the
62
fast kinetic process was followed and represented by Tafel mechanism when two 𝑯𝒂𝒅𝒔
desorb from catalyst surface and combine directly and then release one H2. In contrast
with the slope value of the glassy carbon electrode without MOF coating
(286.63 𝒎𝑽. 𝒅𝒆𝒄−𝟏 ) which take slow kinetics process. The high-speed electrochemical
reactions provided by as prepared MOF catalyst might be interpreted with relation to
MOF porous structure, this permanent porosity promote the diffusion of electrolyte and
mass transfer through the electrochemical process causing the kinetic of these reactions
to be high and lead to increase the efficiency of the system.
Figure 24 Tafel plot of Co.MOF commercial Pt catalyst, and GCE electrode

synthesized catalyst
3.1.1.2.3. EIS-Electrochemical Impedance Spectroscopy for Co.MOF

Electrocatalyst Type:
The interface reactions between electrolyte and electrode were characterized by running
the EIS experiment from high frequency region to low frequency region. EIS Nyquist
63
plot, which displays the imaginary part of impedance against the real part can be
represented as semicircles.
The EIS measurements of as prepared catalyst sample at different potential points were
recorded, as well the same EIS measurements for the Co.MOF sample and Pt catalyst
were measured for compering at a static potential of – 0.25 V to further demonstrate the
following parameters charge transfer resistance 𝑅𝑐𝑡 , solution resistance 𝑅𝑆 and the
coating capacitance 𝐶𝑐 respectively , the obtained Nyquist curve was fitted to the simplex
method model (REAP2CPE),then the important parameters’ numerical values were
extracted.
from the Nyquist plot’s EIS response for the sample at various overpotentials as it
displayed in (Fig 25), the diameter of the semicircles obviously diminished with
increasing overpotential, demonstrating 𝑅𝑐𝑡 decreasing with increasingly negative
electrode potentials. Compatible with (table 7) which display the decreasing of the
numerical values of 𝑅𝑐𝑡 with increase the potentials.
Co.MOF 𝑅𝑆 (Ω) 𝑅𝑐𝑡 ( Ω ) 𝐶𝑐 (µF)
-0.20 17.70 123.7 194.× 10−6
-0.25 18.20 21.39 254.6 × 10−6
-0.28 17.890 2.045 55.8 × 10−6
-0.30 17.98 1.06 7.54 × 10−6
Table 7 Co.MOF decreasing of the numerical values of Rct with increase the potentials.
As exhibited in (Fig 26), commercial Pt catalyst shows lowest charge transfer resistance
𝑅𝑐𝑡 of 2.57ohm, solution resistance 𝑅𝑆 is about 13.1ohm, and the coating capacitance 𝐶𝑐
is about 292.9× 10−6 respectively ,while the Co sample exhibits similarity with Pt
sample’s behaviour with 17.6 ohm for 𝑅𝑆 ,11.7 ohm for 𝑅𝑐𝑡 , and 249.5× 10−6
indicating to clear an improvements of conductivity.
64
Lowering the charge-transfer resistance of the Co.MOF catalyst may be attributed to its
structure contacting with the electrolyte efficiently, and electrons flow was with high
speed during an electrochemical reaction at the electrode-electrolyte interface. This can
be correlated with the structural features of metal organic framework (up to 90% free
volume) providing enormous surface area with high permanent porosity that can facilitate
the electrolyte diffusion and mass transfer during the electrocatalytic process leading to
high conductivity performance (183).
Reducing the solution resistance 𝑅𝑆 of the synthesized sample to get close to 𝑅𝑆 of Pt is

another positive sign about the ionic conductivity of the electrolyte was high (188).
The obtained number for coating capacitance 𝐶𝑐 can be beneficial to demonstrate

Co.MOF coating has the ability to release and store the charge efficiently, besides being
a protective factor for the electrode (188).
Figure 25 EIS measurement for -Co.MOF synthesized catalyst at different overpotential

points.
65
Figure 26 EIS measurement for -commercial Pt catalyst, Co.MOF, Fe.MOF, and
Co.Fe.C.MOF/Co.Fe(A) synthesized catalysts at static overpotential points.
3.1.1.2.4. HER Stability for Co.MOF Electrocatalyst Type:
HER stability of the synthesized electrocatalyst through the hydrogen production by

water electrolysis technique is another significant parameter that we need to insure for
catalytic application. CO.MOF stability at the cathodic area was checked out by running
LSV polarization curve for 100 cycles with a scan rate 5 mV s-1, initial E(V) was recorded
as (0.2V), and final E(V) was recorded as (-0.35 V). as it was displayed from the (Fig 27),
there was no change between the first cycle and the last cycle, suggesting high stable
catalyst structure.
66
Figure 27 Co.MOF polarization curves before and after 100 cycles
3.1.2. Cobalt Calcinated MOF, Cobalt Calcinated and Loaded with Iron and
Cobalt.
3.1.2.1. Linear Sweep Voltammetry Analysis for Co.C.MOF and

Co.C.MOF/Fe.Co Electrocatalyst Type:
Examination the catalytic behaviour of MOF derivatives was done with the similar
procedures of LSV experiment in order to see the effect of the calcination processes and
loading MOF structure with atoms on its function through the cathodic reactions.
The observed overpotential for Co.C.MOF/Fe. Co sample was η10 = 96 mv when current
density at 10 mA.𝒄𝒎−𝟐 and less than Co.C.MOF case which was about η10 = 108 mv at
the same current density it can be seen from the polarization curve in the (Fig 28), these
two cases obtain acceptable reduction on the applied voltage required from the system to
produce hydrogen at the cathodic area, The HER performance of them is comparable to
that of Pt catalyst Similarly, bare GCE. However, Co.MOF without any additional
67
chemical process still act as the most affective and extraordinary catalyst, consequently
the order will be like the following:
Co.MOF (η10 = 50mv) < Co.C.MOF/Fe. Co (η10 = 96 mv) < Co.C.MOF (η10 =108 mv).
Co.MOF calcination process included heating the catalyst structure at high temperature
900° 𝐶 within inert atmosphere and 5h duration , if this chemical treatment was conduct
appropriately with the optimum condition parameters can lead to positive impact to
enhance catalytic performance make it more stable and increase its conductivity , more
precisely this operation leads to lots of structural transformations starting from the whole
frame work collapse and ligand decomposition since the porosity arise from this linker,
the pours structure will be changed or decreased significantly, which in turn play an
important role to decrease the high surface area of our MOF then less catalytic
performance (189). However, cobalt calcinated sample and the calcinated and loaded one
represent applicable case with reducing the system overpotential in our study regardless
to comparing with Co.MOF case and compering with another research.
Another possible explanation might be provided in term of rearrangement of the metal

node leading to change its crystalline structure and its property. This redistribution can
significantly impact positively or negatively MOF conductivity, it may cause the metal
centres to be less or more exposure or available through the electrochemical catalytic
reaction.
As well BIM ligand in case Co.C.MOF that was loaded with Fe and Co, when it collapses
the amount of the metal can be increased and block each other to cause blocked active
site through hydrogen binding through the process due to being intensive and cumulated
within the calcinated structure (189).
68
Figure 28 polarization curve commercial pt, Co.MOF, /Fe ,Co.C.MOF, Co.C.MOF
GCE electrode
3.1.3. Synthesized Fe-MOF Electrocatalyst with Solvothermal Method
3.1.3.1. Structural Characterization of Fe.MOF Electrocatalyst:
3.1.3.1.1. Fourier Transform Infrared (FT-IR) Of Fe.MOF Electrocatalyst:
The formation of as prepared Fe.MOF new molecular structure was confirmed by

employing FT-IR spectroscopy, and the analysing results were displayed in the (Fig 29)
with comparison with BIM alone spectroscopy in order to preform cooperative analyses
that assist to identify the prominent changes in particular vibration modes.
The observed changing can be seen in the C-H stretching vibrations of BIM between
3200-2000cm-1 when it bonds to iron nitrate nonahydrate which will be represented in
prominent decrease in the intensities and peaks broadening due to impact of new metal
coordination with slightly shift in the wavenumbers due to alternating the hydrogen
bonding pattern as a result of a new coordination. Then the following changes were
69
located in the range between 1200-1600cm-1 with also reduction in the intensity of the
absorbing bands which is related directly to the stretching vibration of C–N, C=N, and
C=C as consequences of the alterations in the molecular environment and coordination
geometry, when it comes to form a new complex (190). Finally the most significant
change was noticed at 1006,519 cm-1 and assigned to iron-nitrogen band ,this can give a
main proof that the targeted Fe.MOF electrocatalyst was done perfectly (191) .
Figure 29 FTIR spectra of Fe.MOF sample
3.1.3.1.2. X-Ray Diffraction (XRD) Of Fe.MOF Electrocatalyst:
The crystalline structures of the as-prepared BIM, Co.MOF and Fe.MOF respectively,
were inspected by X-ray diffraction (XRD). As it exhibited in (Fig. 30) where the
diffraction peaks are obviously and sharply appeared to indicate on the growth of well-
crystallized MOFs structure.as it was clarified in this figure the diffraction pattern was
altered due to coordination of metal ions (Co.Fe) into BIM ligand structure, causing the
70
positions and the intensities of the peaks to be changed ,more precisely the intensity of
both cases peaks was decreased indicating to formation of hybrid structure (191).
for iron based catalyst sample the positions and the intensities of XRD diffraction peaks
of BIM were changed completely as it seen in the same figure(green line) to be appeared
at 2θ of 33.20 ,36.01 ,41.01 ,50.5 ,55.01 indicating that iron crystalline nanostructure was
formed appropriately, compering to the related case study where the XRD pattern for
Fe.MOF is similar to this obtained pattern with partially matching points (178).
However, the iron sample exhibit more broadened peaks the thing that indicates on less-
quality crystallites compering to cobalt case, as well the number of peaks was reduced to
be less than the cobalt case.
Figure 30 XRD pattern of BIM, Co-MOF, and Fe-MOF samples
3.1.3.2. Electrochemical Measurements:
3.1.3.2.1. Linear Sweep Voltammetry Analysis for Fe-MOF Electrocatalyst

Type:
Checking the performance of Fe.MOF electrocatalyst toward the cathodic region was
done again by using LSV tool with the similar conditions like the previous case, as well
71
three cases were recorded to compare the catalytic activity as prepared electrocatalyst,
commercial 40 wt. % pt catalyst coated on GCE as a reference, and bare glassy carbon
electrode without catalyst coating, respectively.
As the polarization curves displayed in the (Fig 31), the superior in electrochemical
behaviour was exhibited by Pt catalyst with η10 = 42mv overpotential when current
density reached 10 mA.𝒄𝒎−𝟐 . Noticeably , at the same cathode current outstanding HER
performance was achieved by another synthesized transition metal-based MOF which is
Fe.MOF, the applied voltage was decreased also and the current density increased sharply
to obtain 46 mv overpotential, this value approximately equal to the pt catalyst
overpotential and away from glassy carbon electrode overpotential which is about
560mV, indicating again that the iron MOF type behaves with high efficiency and to its
incredible capability to minimize the applied extra overpotential voltage 𝑽𝒐𝒑 to operate
an extra voltage from the system, clearly similar with cobalt case this considers also one
of the lowest 𝑽𝒐𝒑 between the previously reported HER catalyst. Compering to 2D Ni-
MOF@Pt NSs case study which represent Noble metal-based electrocatalyst with η10
=43mv overpotential when current density reached 10mA.𝒄𝒎−𝟐 and HER Tafel slope
value of 30 mV dec-1(145). Additionally, these will provide great evidence about the
powerful of MOF catalyst structure that was prepared with one type of metal ion and
exceed in its performance the other prepared electrocatalyst such as Fe (OH)x@Cu-MOF
case study represent transition metal-based electrocatalyst with η10 = 112 mv
overpotential when current density reached 10 mA.𝒄𝒎−𝟐 and HER Tafel slope value of
76 mV dec-1 (149). (Table 8) summarize HER performance of the recently reported
transition metal-based MOF and Nobel metal-based MOF in 0.5 M H2SO4 and show
compering with another cases of study.
Iron based MOF measurements remarkably approaches the Nobel metal-based catalyst’s
activity this high catalytic accomplishment can be interpreted by understanding the
chemical properties of the iron metal, iron is considered as one of high-valent metal ions
(high oxidation state between 𝐹𝑒 +3 and 𝐹𝑒 +2 ), more precisely, at the atomic level the
electron configurations of Fe (+3), and Fe (+2) are 1s² 2s² 2p⁶ 3s² 3p⁶ 4s² 3d3, 1s² 2s² 2p⁶
3s² 3p⁶ 4s² 3d4 respectively (1).which leads to form more vacancies in 𝐹𝑒 +3 and 𝐹𝑒 +2
valence shell(empty d orbitals ), in addition the electron affinity of iron is 15.7 kJ/mol ,
72
consequently, the energy needed to release the electrons from the valence shell of the iron
is not too much high, this unique feature make it capable to undergoes the redox reaction
quickly and act as highly active metallic centre through adsorption /desorption process .
B) its ability to have different coordination environments (each oxidation state has
specific electron configurations) which in turn leads to flexibility and versatility in the
Coordination Geometry when it comes to accommodate organic ligand around iron ions
(tetrahedral, octahedral). Which considered as beneficial factor to design such an efficient
catalytical structure with increased surface area and porosity, and finally improve electron
transfer during the electrochemical reaction, this also have a positive impact on incredible
reducing on the resistance parameters through the EIS measurements.
Figure 31 polarization curve commercial pt, Fe.MOF, GCE electrode
73
Electrocatalysts Electrolyte Overpotential (mV) at 10 mA cm􀀀 2 Tafel slope (mV dec-1) Ref
Fe.MOF 0.5 M H2SO4 46 46.71 This work
FeBHT 0.5 M H2SO4 173 119 (184)
Fe (OH)x@Cu-MOF 0.5 M H2SO4 112 76 (149)
Ru-NiFeP/NF 0.5 M H2SO4 29 55.7 (192)
Table 8 summary of HER performance of the previously reported MOF electrocatalyst
3.1.3.2.2. Tafel Slope Analysis for Fe-MOF Electrocatalyst Type:
The high functionality of iron-based metal organic framework catalyst was supported by
Tafel slope again to enable us to investigate the catalytic mechanism of the iron sample,
as (Fig 32) displays that slope was obtained as a numerical value. For comparison the
slope was calculated for iron catalyst, Pt catalyst, and for glassy carbon electrode
respectively. The obtained numbers were 46.71 𝒎𝑽. 𝒅𝒆𝒄−𝟏 for Fe.MOF, taking Volmer–
Heyrovsky mechanism, which is clearly away from the slope value of the glassy carbon
electrode without MOF coating (286.63 𝒎𝑽. 𝒅𝒆𝒄−𝟏 ) which take slow kinetics process.
implying a remarkable cathodic kinetics that close to Pt catalyst mechanistic pathway
with numerical value is about 34.32 𝒎𝑽. 𝒅𝒆𝒄−𝟏 .
This can generate another proof about high HER performance with high kinetic
electrochemical reactions. The high-speed electrochemical reactions provided by as
prepared MOF catalyst might be interpreted with relation to utilization of iron that
consider high-valent metal ions and can perform the electrochemical reaction rapidly,
moreover MOF with porous structure, with increased permanent porosity promote the
diffusion of electrolyte and mass transfer through the electrochemical process causing the
kinetic of these reactions to be high, and lead to increase the efficiency of the system
(193).
74
Figure 32 Tafel plot of Fe.MOF synthesized catalyst, commercial Pt catalyst, , and
GCE.
3.1.3.2.3. EIS-Electrochemical impedance spectroscopy for Fe-MOF

electrocatalyst type:
The EIS measurements of as prepared iron based catalyst sample at different potential
points were recorded, in order to investigate the interface reactions between electrolyte
and electrode, as well the same EIS measurements for the Fe.MOF sample and Pt catalyst
were measured for compering at a static potential of – 0.25 V to further extract the
following parameters charge transfer resistance 𝑅𝑐𝑡 , solution resistance 𝑅𝑆 and the
coating capacitance 𝐶𝑐 respectively , the obtained Nyquist curve represented as
semicircles was fitted to the simplex method model, particularly (REAP2CPE),then the
important parameters’ numerical values were extracted.
75
As it displayed in (Fig. 33), the diameter of the obtained semicircles obviously decreased
with increasing overpotential at various overpotentials from the Nyquist plot’s EIS
response for the sample, demonstrating 𝑅𝑐𝑡 decreasing with increasingly negative
electrode potentials. Compatible with (table 9), which display the decreasing of the
numerical values of 𝑅𝑐𝑡 with increase the potentials.
As it obvious in (Fig 34), commercial Pt catalyst shows lowest charge transfer resistance
𝑅𝑐𝑡 of 2.57ohm, solution resistance 𝑅𝑆 is about 13.1ohm, and the coating capacitance 𝐶𝑐
is about 292.9× 10−6 respectively ,while the Fe sample exhibits similarity with Pt
sample’s behaviour with 7.6 ohm for 𝑅𝑐𝑡 ,and lower than platinum catalyst 3.4 ohm
for 𝑅𝑆 and 1.820× 10−3 for coating capacitance 𝐶𝑐 indicating to clear an improvements
of conductivity. Lowering the charge-transfer resistance of the Fe.MOF catalyst may be
linked to efficient contacting between its structure and the electrolyte, and electrons flow
was with high speed during an electrochemical reaction at the electrode-electrolyte
interface This also can be linked particularly with the structural features of Fe based metal
organic frame work, the high flexibility to accommodate organic ligand( BIM) around
iron metal due to high oxidation state provides enormous surface area with high porosity
,add to that more amount of the aromatic rings that can increase more and more the
electrolyte diffusion and mass transfer during the electrocatalytic process leading to high
conductivity performance, and this was reflected clearly from the small numerical values
of the iron sample 7.6 ohm for 𝑅𝑐𝑡 ,and 3.4 ohm for 𝑅𝑆 .
76
Fe.MOF 𝑅𝑆 (ohm) 𝑅𝑐𝑡 (ohm) 𝐶𝑐
-0.20 3.303 81.40 223.1 × 10−6
-0.21 3.366 7.606 1.820× 10−3
-0.23 3.704 5.518 1.112 × 10−3
-0.26 4.219 12.18 1.040 × 10−3
Table 9 Fe.MOF decreasing of the numerical values of Rct with increase the potentials.
Figure 33 EIS measurement for -Fe.MOF synthesized catalyst at different overpotential

points.
77
Co.Fe.C.MOF/Co.Fe synthesized catalysts at static overpotential points.
3.1.3.2.4. HER Stability for Fe-MOF Electrocatalyst Type:
running LSV polarization curve for 100 cycles with a scan rate 5 mV s-1, initial E(V)
was recorded as (0.2V), and final E(V) was recorded as (-0.35 V) was conduct in order
to check Fe.MOF stability through HER electrochemical process. as it was displayed from
the (fig 35), there was no change between the first cycle and the last cycle, suggesting
high stable catalyst structure that can be associated with high connectivity between iron
metal clusters and benzimidazole ligand (194), as a result the higher connectivity suppress
the ligand dissociation leading to more stable, add to that iron complex with diverse
coordination environments allow for tuning of reactivity and stability through chemical
reactions.
78
Figure 35 Fe.MOF polarization curves before and after 100 cycles
3.2. Synthesis Of Bimetallic -MOF With Different Preparation Methods
3.2.1. Synthesized Co.Fe. MOF Electrocatalyst, Calcination and Metal Loading

(A):
3.2.1.1. Structural Characterization of Co.Fe.C.MOF/Co. Fe(A)

Electrocatalyst:
3..2.1.1.1. Fourier Transform Infrared (FT-IR) of Co.Fe.C.MOF/Co. Fe(A)

Electrocatalyst:
The main changing that were done in the FT-IR spectra for each individual case (Fe.MOF
and Co.MOF) were represented in the (Fig 36) which represent Co.Fe.C.MOF/Co.Fe(A)
as it contains the peaks that indicate to iron-nitrogen bonds at 1101cm-1 471 cm-1
and
cobalt-nitrogen bonds at 3050-3200cm-1, which interpreted the absence of this peak at
iron case, add to that the changing in the range between 3200-2000 cm-1 which is related
directly to C-H stretching vibrations of BIM, however the stretching form now became
79
different from the previous cases due to existence of two metal ions so the stretching
might be like a steady line and the same situation will be at the range 1200-1600cm-1 (C–
N, C=N, and C=C ).remarkably ,the mutual vibrations for the three study cases take place
at 3800-3400cm-1 which is linked to N-H group in the triethylamine, and this might be
compatible with the absence of these vibration in the BIM spectra.
Figure 36 FTIR spectra of Co.Fe.C.MOF/Co.Fe(A) sample.
3.2.1.2. Electrochemical Measurements
3.2.1.2.1. Linear Sweep Voltammetry Analysis for Co. Fe.MOF And Co.
Fe.C.MOF/Fe. Co(A) Electrocatalyst Type.
The electrocatalytic activity of the synthesized bimetallic Co. Fe.MOF(A), Co.

Fe.C.MOF/Fe. Co (A) electrocatalysts toward the cathodic region was checked by using
LSV experiment with the similar system and conditions like the previous cases, as well
80
four cases were recorded to compare the catalytic activity for two of as prepared
electrocatalysts (A), commercial 40 wt. % pt catalyst coated on GCE as a reference, and
bare glassy carbon electrode without catalyst coating, respectively.
With new step that aim to show how reaction time, temperature, are critical to the
performance of the catalysts, bimetallic MOF was prepared with simple and short method
that relay on stirring and heating the reaction mixture for one hour, that means the
duration of heating process was changed from the previous methods to take one hour and
the heating temperature also changed to be 85𝐶 ° , the sample of as prepared Co.
Fe.MOF(A) catalyst was exanimated, as it clearly exhibited in the (Fig 37) Pt based
catalyst contribute with minimum amount of η10 = 42mv overpotential when current
density reached 10 mA.𝒄𝒎−𝟐 . While glassy carbon electrode overpotential is about
560mV, the new catalyst contributes with η10 = 428 mv overpotential indicating to low
HER catalytic activity, in contrast to this case, Co. Fe.C.MOF/Fe.Co (A) type was with
perfect contribution to give η10 = 57 mv overpotential, suggesting noticeable
improvements through the successful calcination and metal loading process. (Table 10)
summarize HER performance of the recently reported transition metal-based MOF and
Nobel metal-based MOF in 0.5 M H2SO4 and show compering with another studies.
The low efficiency of Co. Fe.MOF (A) can be assigned to the reaction time and the
heating temperature were not sufficient to produce such an efficient catalyst because of
the energy required to be provided for the reactant molecules comes in general from
increasing the reaction temperature, in contrast the intensive high temperature negatively
impacts the catalytic efficiency. This can be demonstrated also by similar study that done
to investigate the impact of these parameters (195).
The excellent cathodic efficiency of Co. Fe.C.MOF/Fe. Co (A) type that exceed Co.
Fe.MOF (A) type can be specified to a lot of cooperative factors: A) Co and Fe
coexistence in catalysts can usually bring synergistic effects (189). B) Add to that
calcination and loading process that was done by using more sophisticated CVD device,
with heating temperature 1000𝐶 ° , for 2 h and constant inert nitrogen gas supplying (to
avoid complete combustion of carbonaceous residue) and implementing appropriate
81
amount of BIM ligand as precursors that contain carbon within MOF, all together
represent an appropriate and optimized calcination parameter to be considered.
C) Another factor that can significantly contribute to catalytic activity is the presence of
carbon shell or carbon residue as a result of calcination process. this one can provide more
active canters, increase the overall surface area of the catalysis and as electron donors and
acceptors contributing to electron transfer processes during catalysis, and insure more
thermal and chemical durability to the catalytic system, this can also be clarified in similar
study that show the importance of this carbon residue (149). D) Finally, the remaining
part of the metals that were loaded to the structure may contribute efficiently to provide
more metallic active canters.
Overpotential (mV) at
Electrocatalysts Electrolyte Tafel slope (mV dec-1) Ref
10 mA cm􀀀 2
Co.Fe.C.MOF/Fe. Co(A) 0.5 M H2SO4 57 37 This work
2D/3D MOF [[Co (BIPA)(5-OH-

0.5 M H2SO4 193 77.1 (166-171)
bdc)] (DMF)](54) n
Ni (OH)2/CoNi2S4/NF 0.5 M H2SO4 124 84 (156-161)
MoOx/Ni3S2/NF 0.5 M H2SO4 76 46 (151-155)
Ru@Ni-MOF 0.5 M H2SO4 112 33 (146)
Table 10 summary of HER performance of the previously reported MOF electrocatalyst
82
Figure 37 polarization curve, Co. Fe.MOF(A) Co. Fe.C.MOF/Fe. Co(A), commercial
pt, GCE electrode
3.2.1.2.2. Tafel Slope Analysis for Co. Fe.C.MOF/Fe. Co(A) Electrocatalyst

Type.
Tafel slope was used again to study HER kinetics and to determine the mechanistic
pathway which will be followed by bimetallic catalyst type. (fig 38) shows Tafel slope
values for the sample case, PT catalyst, and for glassy carbon electrode respectively. The
slope value for Co. Fe.C.MOF/Fe. Co (A) was obtained to be 37 𝒎𝑽. 𝒅𝒆𝒄−𝟏 proving
again the high HER kinetics process and high catalytic efficiency to drive the cathodic
reaction rapidly, approximately similar to pt-catalyst which was about 34.32
𝒎𝑽. 𝒅𝒆𝒄−𝟏 this value is represented by Volmer mechanism. As well the bare glassy
carbon electrode without MOF coating was about 286.63 𝒎𝑽. 𝒅𝒆𝒄−𝟏 which take slow
kinetics process. This very small value of the Tafel slope verify that the fast reactions
dynamic indicates to the high improvements that were done on the bimetallic catalyst
through the calcination and metal loading process to obtain such a remarkable particular
83
case study that represents a new strategy to implement MOFs as precursors and promising
attempting to diversified MOF structure with obtaining a new and unique MOF carbon
shell structure. With offering increased number of the metallic active sites that can
accelerate hydrogen adsorption process through the catalytic process.
Figure 38 Tafel plot of Co. Fe.C.MOF/Fe. Co(A) synthesized catalyst, commercial Pt

catalyst, and GCE electrode.
3.2.1.2.3. EIS-Electrochemical Impedance Spectroscopy Co. Fe.C.MOF/Fe.

Co(A) Electrocatalyst Type.
As it clears in (Fig 39), the obtained Nyquist curve for Co. Fe.C.MOF/Fe. Co (A)
represented as semicircles was fitted to the simplex method model, particularly
(REAP2CPE the diameter of the obtained semicircles obviously decreased with
increasing overpotential at various overpotentials from the Nyquist plot’s EIS response
for the sample, demonstrating 𝑅𝑐𝑡 decreasing with increasingly negative electrode
84
potentials. Compatible with (table 11) which display the decreasing of the numerical
values of 𝑅𝑐𝑡 with increase the potentials.
Co.Fe.C.MOF/Fe. Co(A) 𝑅𝑆 (Ω) 𝑅𝑐𝑡 ( Ω ) 𝐶𝑐
-0.21 18.25 12.24 508.5 × 10−6
-0.23 18.07 10.13 1.425 × 10−3
-0.26 17.73 8.83 5.728 × 10−3
-0.30 17.54 2.376 107.8 × 10−6
Table 11 Co. Fe.C.MOF/Fe. Co(A) decreasing the numerical values of Rct with increase
the potentials.
As it obvious in (Fig 40) at a static potential of – 0.25 V when the EIS measurement was
done and the obtained Nyquist curve fitted to the same model, commercial Pt catalyst
shows lowest charge transfer resistance 𝑅𝑐𝑡 of 2.57ohm, solution resistance 𝑅𝑆 is about
13.1ohm, and the coating capacitance 𝐶𝑐 is about 292.9× 10−6 respectively, while Co.
Fe.C.MOF/Fe. Co (A) sample show a good behaviour with 12.24 ohm for 𝑅𝑐𝑡 ,and 18.25
ohm for 𝑅𝑆 and 508.5× 10−6 for coating capacitance 𝐶𝑐 indicating to clear an
improvement of catalyst conductivity through the calcination process that was done
successfully. Reducing the charge transfer resistance might be a noticeable sign about
increase the conductivity at the interface reactions (electrode-electrolyte interface) due to
increase the number of the active metal centres and the synergistic effect between two
kinds of the metal ions and this also can reflect positively on increase the ionic
conductivity of the electrolyte which can be seen obviously from the obtained value of
𝑅𝑆 .
85
Figure 39 EIS measurement for - Co. Fe.C.MOF/Fe. Co(A) synthesized catalyst at different
overpotential points.

Co.Fe.C.MOF/Co.Fe synthesized catalysts at static overpotential points.
86
3.2.1.2.4. HER Stability Co. Fe.C.MOF/Fe. Co(A) Electrocatalyst Type.
The stability of the catalyst sample was checked by running again LSV polarization curve
for 100 cycles, as it displayed from the (Fig. 41) no change between the first cycle and
the last one, assigning to highly thermal and chemical stable structure, that result from
the structural improvements, add to that the optimized calcination process parameters that
lead to high active catalytic structure.
Figure 41 Co. Fe.C.MOF/Fe. Co(A) polarization curves before and after 100 cycles
3.2.2. Synthesized Co.Fe. MOF Electrocatalyst, Calcination and Metal Loading

(B):
3.2.2.1. Linear Sweep Voltammetry Analysis for Co. Fe.MOF And

Co.Fe.C.MOF/Fe. Co(B) Electrocatalyst Type:
This case study represents the effects of metal: ligand ratio and the solvent type of
selection, beside the heating temperature and time factors on the catalyst structure and
activity.
87
With a new attempting to optimize the synthesis process parameters, changing the mount
of initial reactants was done through double the metal source amount and reduce BIM
organic linker amount to the half of previous amount, and using DMF solvent type twice
through the preparation and washing after centrifugation. Then HER electrochemical
catalytic activity was examined by applying the same experiment conditions with using
the same three electrode cell system.
The observed overpotential for sample Co.Fe.C.MOF/Fe. Co (B) was η10 =118 mv when
current density at 10mA.𝒄𝒎−𝟐 and significantly less than Co.Fe.MOF(B) case which was
about η10 =334 mv at the same current density it can be seen from the polarization curve
in the (Fig. 42) Co.Fe.C.MOF/Fe.Co (B) case obtains acceptable and good reduction on
the applied voltage required from the system to produce hydrogen at the cathodic area
compering with Co. Fe.MOF (B) case that was with less activity. The HER performance
of them also compared Pt catalyst and, bare GCE.
Co. Fe.MOF(B) case was synthesized by utilization DMF solvent which is big molecules
and less volatile solvent, these point can affects MOF structure specifically, pore size and
surface area will be smaller than the one that was prepared with two or three types of
solvent ,this in turn affect badly the catalyst efficiency this was shown with related study
that was done to see effect of the solvent mixture on the morphology and electrochemical
properties (196). Moreover washing the catalyst powder after collecting it by
centrifugation was done again by using DMF, so there is no chance to replace the less
volatile DMF solvent with more volatile ethanol solvent through the thermal activation
of the catalyst, and no chance to increase the pore size (182). Add to these points the
reduced amount of the BIM which in turn reduce the porosity of MOF structure and
increase metal ratio and cause the metallic centres to block each other. And finally, the
heating temperature and time that was discussed in the previous case.
Co.Fe.C.MOF/Fe. Co(B) with η10 =118 another proof about the significance of the
calcination process to improve the catalytic performance regardless to the metal: ligand
ratio and ignoring the type of solvent since it will be removed totally during the high
calcination process.
88
Co.Fe.C.MOF/Fe.Co (A) case study (different metal: ligand ratio and calcination
parameters 1000𝐶 ° , 2ℎ,and more advanced device that offer more controllable inert
atmosphere) with η10 =57 mv overpotential, compering to Co.Fe.C.MOF/Fe.Co (B) case
study (different metal: ligand ratio and calcination parameters 900𝐶 ° , 5ℎ ) with η10 =118
mV overpotential still considered as better case study.
Figure 42 polarization curve, Co. Fe.MOF(B) Co. Fe.C.MOF/Fe. Co (B), commercial

pt, Fe.MOF, GCE electrode
3.3. Comparison Of Electrochemical Measurements for All MOFs Synthesized

Electrocatalyst Types.
3.3.1. Comparisons Of Linear Sweep Voltammetry Analysis and Tafel Slope
The final polarization curve which is displayed in the (Fig. 43), represent the whole scene
of this research study, showing the whole synthesized MOFs electrocatalyst types. What
was done staring from preparation of mono types such as Co.MOF and Fe.MOF, then
trying to preform calcination and metal loading to these types and then navigating to new
attempting to diversified MOF structure with more than one type of metal ions with new
89
simple methods that include changing a lot of parameters, and finally successful trying to
manipulate this diversified structure through changing calcination parameters and
conditions and so on.
The best scenario was with mono metallic MOF with Fe.MOF η10 = 46 mv overpotential
and Co.MOF η10 = 50 mv overpotential, as well the (Fig. 44) show Tafel slope values
for all best three cases.
Acceptable and good performance for Co.C.MOF with η10 = 96 mv overpotential and
Co.C.MOF/Fe. Co with η10 =108 mv overpotential.
Another two cases were represented with method (A) and (B) with lowering the
overpotential from η10 = 428 mv overpotential for Co. Fe.MOF(A) to η10 = 57 mv
overpotential for Co. Fe.C.MOF/Fe.Co (A) case study, and from η10 = 334 mv for Co.
Fe.MOF (B) to η10 =118 mv for Co.Fe.C.MOF/Fe.Co (B).
The general order for the HER catalytic efficiency for all synthesized types of MOFs in
this research study will take the following order:
Commercial Pt η10 =42 mv> Fe.MOF η10 =46 mv > Co.MOF η10 =50 mv > Co.
Fe.C.MOF/Co. Fe (A) η10 =57 mv > Co.C.MOF/Fe. Co with η10 =96 mv>
Co.C.MOF η10 =108 > Co.Fe.C.MOF/Fe. Co(B) η10 =118 mv> Co. Fe.MOF(B) η10
=334 mv > Co. Fe.MOF(A) η10 =428 mv> GCE electrode η10 =560 mv.
Consequently, the following configuration for the obtained Tafel slope value:
Pt=34.32 𝒎𝑽. 𝒅𝒆𝒄−𝟏 > Co. Fe.C.MOF/Co. Fe (A)= 37.01 𝒎𝑽. 𝒅𝒆𝒄−𝟏 >
Co.MOF=38.57 𝒎𝑽. 𝒅𝒆𝒄−𝟏 >Fe.MOF=46.71 𝒎𝑽. 𝒅𝒆𝒄−𝟏 > >GCE electrode= 286.63
𝒎𝑽. 𝒅𝒆𝒄−𝟏
And the following (Table 12) (189), exhibit the overpotential obtained values for all of
MOF’s types with Tafel slope values.
90
Co.
Co.C.M Co.Fe.C.M Co.
Fe.M Co. Fe.C.MO Co.C. Co.Fe.C. GC
Pt OF/Fe. OF/Fe. Fe.MO
OF MOF F/Co. Fe MOF MO(A) E
Co Co(B) F(B)
(A)
η10/ mv 42 46 50 57 96 108 118 334 428 560
Tafel
34. 46.7 286
slope 38.57 37.01 _____ _______ _________ ______ ____
32 1 .63
𝑚𝑉. 𝑑𝑒𝑐 −1
Table 12 the overpotential obtained values for Pt, Fe.MOF, Co.MOF, Co.
Fe.C.MOF/Co. Fe (A), Co.C.MOF, Co.C.MOF/Fe. Co, Co.Fe.C.MOF/Fe. Co(B), Co.
Fe.MOF(B), Co.Fe.C.MO(A) and GCE
Figure 43 polarization curve for Pt, Co.MOF, Co.Fe.C.MOF/Co.Fe (A), Co.C.MOF,

Co.C.MOF/Fe. Co, Co.Fe.C.MOF/Fe. Co(B), Co. Fe.MOF(B), Co.Fe.C.MO(A), GCE.
91
Figure 44 Tafel slope values for Pt, Co.Fe.MOF/Fe.Co (A), Fe.MOF, Co.MOF
3.3.2. EIS-Electrochemical Impedance Spectroscopy Analysis
The following (table 13) show the obtained numerical values for EIS parameters and (Fig
45) display the EIS measurements for all of MOF’s type.
Applied
𝑅𝐶𝑇 𝑅𝑠
Electrocatalyst Overpotential Coating capacitance
(Ω) (Ω)
mV
Pt 42 2.569 13.99 292.9 × 10−6
Fe.MOF 46 7.606 3.366 1.820 × 10−3
Co.MOF 50 11.69 17.59 249.5 × 10−6
)Co.Fe.C.MOF/Co. Fe(A) 57 12.24 18.25 508.5 × 10−6
Table 13 the obtained numerical values for EIS parameters for Pt, Fe.MOF, Co.MOF,
Co.Fe.C.MOF/Co. Fe(A)
92
Figure 45 EIS measurements for Pt, Co.MOF, Fe.MOF, Co.Fe.MOF/Fe.Co (A)
th e overp oten tia l ob tain ed valu es an d Tafel slop e for MOFs typ es
GCE 286.63
560
Co.Fe.C.MO(A) 0
428
Co. Fe.MOF(B) 0
334
Co.Fe.C.MOF/Fe. Co(B) 0
118
Co.C.MOF/Fe. Co 0
108
Co.C.MOF 0
96
Co. Fe.C.MOF/Co. Fe (A) 37.01
57
Co.MOF 38.57
50
Fe.MOF 46.71
46
Pt 34.32
42
0 100 200 300 400 500 600
Tafel slope η10/ mv
Figure 46 the overpotential obtained values for synthesized MOFs types and Tafel slope
93
4. CONCLUSION
As a summary of this scientific work metal organic framework that relay on transition
metal was successfully synthesized, developed, characterized, and perfectly assessed in
their performance by using powerful analytical tools.
Different types of MOFs were prepared at lab area, the research plan included conducting
two methods solvothermal method and simple heating and stirring, these were done with
changing the solvent types, heating temperature and time, and the ratio between metal
and ligand. Then by using CVD device calcination and metal loading were performed as
an additional process to enhance the catalytic functionality. Characterization of MOFs
structure was done through FT-IR and XRD technique and the success in formation the
catalyst types was confirmed and interpreted appropriately through the discussion part to
add to this work meaningful evidence about getting the right structure of these new
materials. Versatile analytical tools such as LSV, Tafel slope, EIS and the stability
measurements enable us to make vital assessments to the HER electrochemical
performance of the MOFs catalyst.
Our initial target in this work was finding an alternatives to platinum catalyst which is
rare and too expensive, and has the highest efficiency for cathodic area within the
electrochemical cell, the major significance of this work study is reporting on the new
types of electrocatalyst that are competitive with Pt ,through successfully synthesizing
transition metal-based MOF as a highly efficient electrocatalyst with two distinctive case
study the first one shows the success in finding monometallic MOF catalysts with similar
performance to the Pt catalyst without any additional chemical process (remarkable
success through the preparation method its self), and the second case shows the
importance of the calcination process parameters to enhance the catalytic activity
(Co.Fe.C.MOF/Co. Fe(A)), (represent noticeable success in optimizing well the
calcination process with effective parameters).
Extraordinary accomplishment was done through the best three cases of study Co.MOF,
Fe.MOF, and (Co.Fe.C.MOF/Co.Fe (A), with their catalytic ability to lowering the HER
overpotential to η10 =50mv,46mv, and 57 mv respectively with Tafel slope values
38.57 𝒎𝑽. 𝒅𝒆𝒄−𝟏 46.71 𝒎𝑽. 𝒅𝒆𝒄−𝟏 ,37.01 𝒎𝑽. 𝒅𝒆𝒄−𝟏 respectively, and finally.
94
resistance of charge transfer 𝑅𝐶𝑇 (Ω) to be 17.59ohm, 3.366ohm, and 18.25ohm
respectively. Clearly these values were highly competitive with commercial Pt-catalyst
where η10=42mv of overpotential with Tafel slope about 34.32 𝒎𝑽. 𝒅𝒆𝒄−𝟏 ,and 𝑅𝐶𝑇 (Ω)
about 2.569 ohm. Consequently, the synthesized MOFs have a great effect to enhance
HER performance of the water electrolysis to produce hydrogen efficiently, finally MOFs
catalysts showed great stability after running LSV polarization curve for 100 cycles.
This research study represents one of the most successful studies that were done and
mange to report lowest achieved overpotential at all since we manage to break off the
limitation for finding available and inexpensive catalysts that are competitive with
platinum catalysts that represent the major obstacles (being expensive and rare) that
hamper the development of more and more sophisticated hydrogen production systems.
95
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114
AUTOBIOGRAPHY
Name-Surname: KİNDA JOUNA VETTI
Educational Background:
• MSc: Marmara University, Institute of Science, Chemical Engineering

Program (2022-2024), GPA 3.93/4.00
• Uskudar University, Faculty of Engineering and Natural Science, Chemical

Engineering Department, Chemical and Biological Engineering Program (2017-
2021). GPA 3.72/4.00 (High Honours)
• BSc: Bachelor Degree in Applied Chemistry, Aleppo University, Faculty of

Science (2005-2 010).
115

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MARMARA UNIVERSITY

I N S TIT UTE F O R G RAD UATE S T U D I E

SYNTHESIS, OPTIMIZATION, AND CHARACTERIZATION

OF METAL-ORGANIC FRAMEWORKS (MOF)

AS EFFICIENT ELECTROCATALYSTS FOR HYDROGEN PRODUCTION

KİNDA JOUNA VETTİ

Department of Chemical Engineering

Prof. Dr. Atıf KOCA

I N S TIT UT E F O R G RAD UATE S T U D I E

SYNTHESIS, OPTIMIZATION, AND CHARACTERIZATION

OF METAL-ORGANIC FRAMEWORKS (MOF)

AS EFFICIENT ELECTROCATALYSTS FOR HYDROGEN PRODUCTION

KİNDA JOUNA VETTİ

Department of Chemical Engineering

Prof. Dr. Atıf KOCA

Prof. Dr. Atıf KOCA (Danışman)

Marmara Üniversitesi .....................................................................(İMZA).................

İstanbul Üniversitesi .......................................................................(İMZA).................

Fen Bilimleri Enstitüsü Müdürü

Prof. Dr. Bülent EKİCİ

Prof. Dr. Atıf KOCA (Advisor)

Marmara University ..........................................................................(SIGN) ...............

Director of the Institute

Prof. Dr. Bülent EKİCİ

I am deeply grateful to Prof. Dr. Atıf KOCA, my supervisor, whose unwavering

I owe an immense debt of gratitude to my steadfast companion and best

To my cherished family members my father M. Khaldoun JOUNA, beloved

January 2024 Kinda Jouna VET

FTIR Structural characterization technique of the as prepared electrocatalysts has been

The significance of this scientific work will be represented in successfully synthesizing

This research area mainly concentrated on developing hydrogen production system by

Synthesizing different types of these nanoparticles such as Co.MOF, Fe.MOF as a

Structural characterization of the as prepared electrocatalysts have been performed by

𝑬(𝑹𝑯𝑬) : Obtained Potential of The Reversible Hydrogen Electrode

𝑬𝑨𝒈/𝑪𝒍 : The Obtained Values of Working Potential

𝜼 𝟏𝟎 : Overpotential At 10 Current Densities

𝑪𝒅𝒍 : Double Layer Capacitance

Ag/AgCl: Silver/Silver Chloride Electrode

𝑹𝒄𝒕 : Charge Transfer Resistance (Ohm)

𝑹𝒔 : Solution Resistance (Ohm)

𝑽𝒂𝒑𝒑 : Applied External Potential (V)

MOF : Metal Organic Frame Work

Co.MOF : Cobalt Based Metal Organic Frame Work

Fe.MOF : Iron Based Metal Organic Frame Work

Co.C.MOF : Cobalt Calcinated Based Metal Organic Frame Work

EIS : Electrochemical Impedance Spectroscopy

LSV : Linear Sweep Voltammetry

HER : Hydrogen Evolution Half Reaction

GCE : Glassy Carbon Electrode

TEM : Transmission Electron Microscopy

SEM : Scanning Electron Microscopy

XPS : X-Ray Photoelectron Spectroscopy

XRD : X-Ray Diffraction

FT-IR : Fourier Transform Infrared

TOF : Turn Over Frequency

FIGURE 1 THE SPECTRUM OF H2 PRODUCTION PROCESSES ................................................ 2

FIGURE 5 ILLUSTRATION OF MOF’S BUILDING BLOCKS AND RESULTING POROUS,

FIGURE 6 MOFS RESULTING FROM DIFFERENT METAL NODES AND BRIDGING

FIGURE 7 DIFFERENT METHODS OF MOF SYNTHESIS, (A) SONO-CHEMICAL SYNTHESIS

METHOD, (D) IONO-THERMAL PROCESS METHOD, (E) MICROWAVE SYNTHESIS