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Review Article
Photocatalytic water splitting for hydrogen production
Rama Devi Tentu and Suddhasatwa Basu∗
As global warming is becoming a pressing issue, H2 as an also releases greenhouse gases. Alternate hydrogen pro-
alternative clean fuel has gained importance. The utilisation of duction utilising resources like nuclear, biomass, solar and
solar energy for water splitting paves a way for environmentally wind are also being explored [1]. The hydrogen produc-
friendly H2 generation. The review discusses recent tion through the above mentioned processes suffers from
developments in photocatalytic water splitting for H2 efficiency losses due to use of electricity for electroly-
production with conjugated polymers, g-C3 N4 , graphene, other sis of water [2• ]. Development of efficient processes to
carbon-based photocatalysts, earth-abundant metal-based utilise naturally available solar energy directly to generate
photocatalysts and co-catalysts. The need for inexpensive, hydrogen by water splitting using solar energy has, thus,
non-toxic, corrosion resistant and earth-abundant emerged as a strong contender [3]. Water splitting essen-
material-based photocatalyst has been emphasised. Strategies tially refers to electrolysis of water i.e. reduction of water
for performance enhancement and development in field of to hydrogen at cathode and oxidation to oxygen at anode.
photocatalytic reactors for H2 production are reviewed. The
importance of design of photocatalyst along with Semiconductor materials acting as photocatalysts absorb
photocatalytic reactor, challenges related to efficiency of photons from the visible spectrum of light (380 nm–
photocatalytic process and assessment and comparison of 700 nm) and the excited electrons from the valence band
activities of photocatalysts for scalable and economically jump to conduction band creating holes in valence band.
viable H2 generation are highlighted. The photo-induced electrons and holes transport to the
catalyst surface and participate in reduction and oxidation
Address
of adsorbed water molecules [4• ]. Each of the steps in-
Department of Chemical Engineering, Indian Institute of Technology
Delhi, New Delhi 110016, India volved in photocatalytic water splitting play a critical role
in determining the overall efficiency for hydrogen pro-
∗
Corresponding author: Basu, Suddhasatwa (sbasu@iitd.ac.in) duction. Light harvesting, charge separation, charge trans-
port, charge utilisation and surface adsorption capacity are
Current Opinion in Electrochemistry 2017, 5:56–62
the steps that influence the photocatalytic quantum ef-
ficiency. Thus, design of photocatalyst to engineer the
This review comes from a themed issue on Fuel cells and electrolyz-
ers
desired properties has been the current research focus.
To utilise solar energy for water splitting either photo-
Edited by Paul Shearing
catalysis (PC) or photoelectrolysis (PEC) can employed.
For a complete overview see the Issue and the Editorial The main difference between the two pathways is that
Available online 16 October 2017 PEC uses additional electrical energy apart from photon
https://doi.org/10.1016/j.coelec.2017.10.019 energy. State-of-the-art photoelectrochemical systems re-
port solar to hydrogen conversion (STH) efficiencies of 2
2451-9103/© 2017 Elsevier B.V. All rights reserved.
to 3%. STH efficiency for photocatalytic systems is as low
as 0.1% because of lower light harvesting capacity [5•• ].

Designing a highly efficient photocatalyst is not sufficient.

Limitations arising due to scaling up from laboratory to pi-
lot reactor demands low cost photocatalysts that can be
Introduction either earth-abundant or be made from earth-abundant
With growing focus on mitigation of climate change, the materials. Stability, recyclability and corrosion resistance
pressure to reduce greenhouse house gases has been in- of photocatalyst in the redox environment is crucial for
creasing since. Various countries pledged to put in efforts large scale hydrogen production [6•• ]. Ultimately photo-
to limit greenhouse gas emissions. On the other hand, catalyst integration into a reactor requires unique reactor
meeting energy needs is critical as human development design configuration to (i) incorporate solar energy input,
index depends on per capita energy consumption. Thus, (ii) carry out photocatalytic reaction, (iii) separate reaction
not only fossil fuel utilisation for energy requirements products and (iv) store or transport fuels obtained [7• ,8].
need to be reduced but also be replaced by cleaner fu- For large scale H2 production, efficient utilisation of so-
els. Hydrogen is an ideal clean fuel of the future. Cur- lar energy in limited space is an issue that needs to be
rent commercial hydrogen production relies on steam re- addressed by reactor design. The attention on photocat-
forming of hydrocarbons mainly obtained from fossil fu- alytic reactor design is comparatively low despite the in-
els. Not only is this process highly energy intensive but terdependence between reactor design and photocatalyst.

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 Water splitting Tentu and Basu 57

Figure 1

Desirable properties of photocatalyst for commercially viable H2 production.

Evaluation of photocatalyst for hydrogen is abundant, inexpensive, non-corrosive, stable and envi-
evolution ronment friendly [11,12]. However, it cannot utilise visi-
Various criteria have been used to evaluate the per- ble light spectrum as its band gap (3.2 eV) lies in UV re-
formance of a photocatalyst. Typically for PEC wa- gion. The extent of solar energy utilised strongly depends
ter splitting and hydrogen evolution reaction (HER), on the region of light spectrum in which photocatalyst
activity is reported in terms of H2 evolution rate is active. Up to 400 nm, the solar conversion efficiency is
(μmol hr−1 g−1 catalyst ) or current density (mA cm−2 ) [9• ]. just 2% similar to the efficiencies observed in photosyn-
For PC systems, time-based HER and H2 –O2 stoichiom- thetic system in plants. Moving to 600 nm the efficiency
etry are parameters that need to be reported [10•• ]. Acar improves to 16% and 32% when extended up to 800 nm
et al. ranked 49 photocatalysts based on their band gap, [4• ,13]. The choice of photocatalyst to exploit the visi-
quantum yield and hydrogen production [6•• ]. These ble light regime and near infrared region, thus, becomes
photocatalysts are selected from literature such that hy- crucial [15• ]. Oxides, sulphides and nitrides of d0 or d10
drogen production reported used similar reactor vessels, transition metal cations have been most widely used as
light sources, filters and temperatures. Standard condi- photocatalysts for water splitting. Some of them include
tions for hydrogen production are essential to evaluate photocatalysts like CdSe, CdS, Ta3 N5 , TaON, C3 N4 , SiC,
the performance enhancement while reporting the effi- BiVO4 , WO3 , Cu2 O, Fe2 O3 etc. [10•• ]. The performance
cacy of the photocatalyst. Other parameters like quantum of metal oxides like WO3 , BiVO4 and Fe2 O3 is limited by
yield (QY), apparent quantum yield (AQY), incident pho- low light harvesting, high charge recombination rates and
ton to current efficiency (IPCE) and absorbed photon to poor charge transport. The conduction band edge position
current efficiency (APCE) are used to evaluate the extent of BiVO4 makes it unsuitable for HER. Although Cu2 O
of solar energy utilised for water splitting or HER by nor- has a theoretical 18% solar-to-fuel conversion efficiency, it
malisation with respect to light intensity and area. The is susceptible to self-reduction in aqueous solution. Simi-
STH efficiency is another parameter commonly reported larly, CdS is susceptible to self-oxidation [14• ]. The pho-
to indicate the hydrogen evolved in PEC cells under air tocatalytic activity of TiO2 and CdS-based photocatalysts
mass 1.5 global (AM 1.5 G) illumination. IPCE and STH have been tabulated in Table 1. Investigation on earth-
is most commonly reported due to ease in measurement abundant and metal-free catalysts like g-C3 N4 , C3 N3 ,
of variables involved [10•• ]. C5 N3 , C10 N3 , boron-based B4.3 C and B13 C2 , graphene,
graphene oxide, carbon nanotubes and carbon quantum
Material development dots has been illustrated in reviews [5•• ,15• ]. Recent
Exploiting properties of elements across the periodic ta- literature has focussed extensively on non-metal-based
ble, a variety of semiconductors have been found to be photocatalysts synthesised from earth-abundant materi-
capable of HER, oxygen evolution reaction (OER) or wa- als owing to challenges of potential cost reduction during
ter splitting. Figure 1 depicts required properties in a scale up. Figure 2 gives a summary of the photocatalysts.
photocatalyst for viable use at large scale. TiO2 is the A brief overview of current status and challenges of conju-
most widely studied photocatalyst for water splitting. It gated polymers, graphene, g-C3 N4 and other inexpensive

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Current Opinion in Electrochemistry 2017, 5:56–62

58
Fuel cells and electrolyzers
Table 1

Summary of the photocatalytic activity of various photocatalysts for water splitting.

Photocatalyst Co-catalyst Photocatalyst Reactant solution and Light source Activity AQY (%) Stability Ref. (Year)
used amount sacrificial agents (hours)
Polymer P7 Pt 25 mg 7.5 ml water, 300 W Xe Lamp with 116 µmol h−1 g−1 0.0225 65 [30] 2016
trimethylamine (TEoA) >420 nm cutoff
7.5 ml, methanol 7.5 ml filter
TFPT-covalent Pt 5 mg 1 ml TEoA, 9 ml water 300 W Xe Lamp with 1970 µmol h−1 g−1 2.20 N/A [31] 2014
organic framework 420 nm < λ < 900 nm
cutoff filter
NiS/Zn0.5 Cd0..5 S RGO, NiS 50 mg 80 ml water, 0.35 M Na2 S, – 375.7 µmol h−1 31.10 12 [32] 2014
/RGO composite 0.25 M Na2 SO3
NGO-QDs – 1.2 g 200 ml aqueous solution, 300 W Xe Lamp with 0.5 µmol h−1 N/A 72 [25] 2014
pH = 3 420 nm < λ < 800 nm
cutoff filter
Hollow C3 N4 3 wt % Pt 20 mg 100 ml aqueous solution, 300 W Xe lamp 275 µmol h−1 N/A 16 [33] 2014
nanosphere 10% TEoA
g-C3 N4 /carbon NiS 50 mg 15 ml TEoA, 85 ml distilled 300 W Xe Lamp 992 µmol h−1 g−1 N/A 15 [34] 2015
black/NiS water with > 420 nm
cutoff filter
mpg-g-C3 N4 /CNT/NiS NiS 50 mg 90 ml water, 10 ml TEoA 300 W Xe lamp 521 uµmol h−1 g−1 N/A N/A [35] 2015
composites
3 wt % P3TH-g-C3 N4 1 wt % Pt 300 mg 600 ml aqueous solution, 300 W Xe Lamp 560 µmol h−1 2.90 N/A [36] 2011
composite 0.25 M Na2 S, 0.25 M with > 420 nm
Na2 SO3 M cutoff filter
Hydrogenated ZnO – 1.64 gm 100 ml aqueous solution, 300 W Xe lamp 122,500 µmol h−1 g−1 N/A 30 [37] 2012
nanorods arrays 0.1 M Na2 SO3 , 0.1 M
Na2 SO3
Cu1.94 S–Znx Cd1-x S Pt 20 mg 50 ml DI, 0.1 Na2 S, 0.1 M 300 W Xe lamp 13,533 µmol h−1 g−1 26.40 N/A [38] 2016
Na2 SO3 with > 420 nm
cutoff filter
CdS/ZnS core-shell – 1 mg 20 ml aqueous solution 300 W Xe lamp 239 µmol h−1 mg−1 16.80 46 [39] 2015
with > 420 nm
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cutoff filter
Si, Fe co doped TiO2 – 400 mg 540 ml distilled water, 500 W Xe lamp 320 µmol h−1 g−1 N/A N/A [40] 2013
60 ml ethanol
 Water splitting Tentu and Basu 59

Figure 2

Overview of recently reported inexpensive earth-abundant material-based photocatalysts.

photocatalysts for application in H2 production has been Carbon-based photocatalyst

presented below. Carbon-based g-C3 N4 , graphene, carbon nanotubes
(CNTs) and other related materials have been reported
as low cost metal free photocatalysts. Several advan-
Conjugated polymers, organic polymers tages associated with g-C3 N4 include ideal band edge
Conjugated polymers are emerging as contenders to scal- positions for water splitting, thermal and chemical sta-
ing up photocatalytic processes owing to their robust- bility and ease of synthesis from earth-abundant low
ness, non-toxicity, visible light activity and relative ease cost precursors. However pristine g-C3 N4 depicts low
in tuning physiochemical properties by manipulation in activity as compared to conventionally used TiO2 photo-
composition, architectures and optical-electronic proper- catalyst. The order of magnitude of activity lies around
ties. This class of photocatalysts includes linear poly- 500 μmol hr−1 g−1 in presence of co-catalysts and sac-
mers, planariser polymers, triazine/heptazine polymers, rificial agents. High recombination rates, low surface
pyrene and bipyridile, benzothiadiazole polyimide-based area and grain boundary effect limit the performance
imine-linked conjugated poly(azomethine) networks, co- of g-C3 N4 [18]. Modulation of precursors and reaction
valent organic frameworks and covalent triazine-based parameters involved in synthesis influences crystallinity,
frameworks. AQY reported ranges from 0.015 to 38.8% defects, surface area and optical-electronic properties.
at λ = 420 nm and HER up to 1970 μmol hr−1 g−1 To further utilise the theoretically available surface area,
for TFPT covalent organic framework has been re- exfoliation by chemical, mechanical, sonication assisted
ported. The reaction conditions, as presented in Table 1, and hydrothermal treatment have been reported that
for TFPT and polymer P7 includes presence of sacri- improve charge transport and charge separation [19• ].
ficial agents and co-catalyst for boosting catalytic per- Morphological modifications with or without templates to
formance [16]. Strategies to modify conjugated proper- create porous g-C3 N4 , hollow spheres and nanostructures
ties of polymer through alternate synthesis routes, chain increase active sites for reaction, specific surface area and
length manipulation, heteroatom substitution, hybridisa- charge mobility [20]. Elemental and molecular doping
tion, heterojunction, nanostructure and sensitisation can are typical strategies for altering optical and electronic
be employed to improve activity of the conjugated or- properties of g-C3 N4 . Heterojunction/composites with
ganic polymers. There is a critical need to address poor g-C3 N4 are widely reported in literature owing to en-
dispersion, durability and rapid charge recombination hancement in charge separation efficiency [21,22]. The
[17]. improvement in performance of g-C3 N4 as a photocat-

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60 Fuel cells and electrolyzers

alyst for H2 generation is requisite if g-C3 N4 has to be earth-abundant co-catalysts for electrochemical as well as
employed in large scale photocatalytic reactor. PEC water splitting has been reported in literature [41].
Co-catalysts coupled with semiconductors are responsi-
Graphene is yet another metal free material that can be ble for (i) lowering activation energy or over-potential
synthesised from earth-abundant carbon containing com- at the surface of semiconductor for HER and/or OER
pounds like graphite. It can act as a charge transporter, (ii) charge separation at the interface of semiconduc-
co-catalyst, photosensitiser and photocatalyst. Graphene tor and co-catalyst interface (iii) supress photo-corrosion
has thus been coupled with photocatalysts as a substitute [6•• ].
for expensive noble metal co-catalyst [23]. The unique
properties of graphene or chemically modified graphene Performance enhancement strategies
(graphene oxide (GO) or reduced graphene oxide (RGO)) Recent work on strategies for enhancing photocat-
include high thermal and electrical conductivity, superior alytic performance include heterojunction formation [42],
charge mobility, high-specific surface area and greater ad- nanostructure design [39], co-catalysts utilisation [41], dye
sorption capacity. Graphene has been reported to improve sensitisation [43], surface plasmonic enhancement [34],
HER and QY when used as co-catalyst or in composite doping [25,27,40] and defect control [17]. Novel methods
with other photocatalysts. Pristine graphene is a conduc- for synthesis, surface modifications and chemical treat-
tor, however, functionalisation, composition engineering, ments specific to composition of photocatalysts also con-
heteroatom doping, size modulation, chemical and mor- tribute to increased photocatalytic activity. However the
phological modifications can tune its electronic proper- patterns may not be replicated in generic photocatalytic
ties as suitable for photocatalyst [24]. N-doped GO quan- systems due to their specific nature. In depth mechanistic
tum dots (NGO-QDs) reported with a band gap of 2.2 eV and theoretical understanding of working of the strategies
was capable of water splitting in the visible light region would pave a way towards systematic applications to pho-
[25]. Challenges to fully utilise the excellent structural tocatalytic systems. This would enable significant jump in
and electronic properties of graphene remains as semi- performance rather than incremental reports with respect
conductor standalone graphene-based materials need fur- to improvement.
ther development to achieve H2 production rates com-
parable to even g-C3 N4 as reported values are under Photocatalytic reactors
100 μmol hr−1 g−1 . The photocatalytic activity of g-C3 N4 The photocatalytic reactions can be carried out in vari-
and graphene-based photocatalysts has been discussed in ous types of reactors depending on configuration of light
Table 1. source used, hydrodynamics of reactants and products as
well as mode of usage of photocatalyst. Some of the reac-
CNTs, fullerenes (C60 ), carbon nanodots, carbon quan- tors reported in literature include thin film reactor system
tum dots and boron carbides are amongst other carbon- [44], moving bed [45], fluidised beds [46] and parabolic
based photoactive materials reported in literature. Liu trough reactors [47]. Development as well as modelling
et al. demonstrated photocatalytic performance of B4.3 C of reactors have been reported in recent literature [7• ,48].
and B13 C for hydrogen production in water–methanol Lasa et al. have developed a centrally irradiated concen-
mixtures used as sacrificial agents [26]. The hydrogen pro- tric slurry photocatalytic reactor. They have also reported
duction rate for B4.3 C and B13 C were 14.5 μmol hr−1 g−1 QY and photochemical thermodynamic efficiency factors
and 4.5 μmol hr−1 g−1 respectively. Wang and co-workers to be considered for calculation of efficiency for this re-
reported synthesis of B–C–N alloys as a photoactive mate- actor [7• ]. Hydrodynamic and radiation absorption mod-
rial for water splitting applications [27]. CNTs, fullerenes elling of a compound parabolic collector using CFD has
(C60 ), carbon nanodots, carbon quantum dot can be used been recently reported by Yuxun et al. [48] The focus on
in conjunction with photocatalysts or photocatalysts com- reactor development has been less compared to the pho-
posites as electron acceptor and transporters, photosensi- tocatalyst development.
tisation and co-catalyst to enhance activity for solar to H2
production [15• ]. Perspectives
The choice of photocatalyst and strategies to improve
Other earth-abundant material-based performance is one of the aspects to be considered for
photocatalysts and co-catalysts achieving higher H2 production. However, recyclability,
Literature reviews of state-of-the-art photocatalysts based reusability and stability become critical factors when con-
on metal oxides and nitrides, ternary oxides [9• ], tran- sidering photocatalysts for industrial applications. Re-
sition metal-based phosphides [28] and chalcogenides cyclability and reusability of photocatalyst with mini-
[29] as well as photocathode materials [14• ]. Precious mum losses ensures that photoactivity remains almost
metals like Pt, Ru, Rh, Os, Pd, Ir have been widely same in each cycle. However difficulty in separation
used to improve STH efficiency. However use of the from aqueous system, deactivation and agglomeration
above expensive co-catalysts at large scale would pose can make the photocatalyst non-reusable. Photostabil-
as cost constraint. Recent progress in development of ity of semiconductor-based photocatalysts also impacts

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 Water splitting Tentu and Basu 61

Figure 3

Summary of factors effecting H2 production efficiencies and controlling parameters to improve the same.

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