PBA Encyclopedia

Received: 31 January 2023 | Accepted: 5 April 2023
DOI: 10.1002/cnl2.64
REVIEW
Hollow structures Prussian blue, its analogs, and

their derivatives: Synthesis and electrochemical
energy‐related applications
Ying Wei1 | Mingbo Zheng2 | Wei Zhu1 | Huan Pang1

1
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu, China
2
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing, Jiangsu, China
Correspondence
Huan Pang, School of Chemistry and Abstract
Chemical Engineering, Yangzhou Electrochemistry is an effective way to obtain clean energy and alleviate
University, Yangzhou 225002, Jiangsu,
China.
energy crisis. Compared with solid structures, hollow structures show a larger
Email: huanpangchem@hotmail.com and specific surface area and expose more active sites. Therefore, when applied to
panghuan@yzu.edu.cn the field of electrochemistry, hollow structures can usually show more
Mingbo Zheng, College of Materials excellent performance. Because of their unique compositions, Prussian blue
Science and Technology, Nanjing
University of Aeronautics and and its analogs (PB/PBAs) usually contain two or more kinds of metallic
Astronautics, Nanjing 210016, Jiangsu, elements, and the synergistic effect between the different metallic elements
China.
provides more possibilities for their application in the field of electrochem-
Email: zhengmingbo@nuaa.edu.cn
istry. After easy treatment of PB/PBAs, derived materials, such as transition‐
Funding information metal oxide, transition‐metal phosphide, transition‐metal sulfide, and so forth
Natural Science Foundation of Jiangsu
can be obtained. Due to the particularity of PBA composition, these derived
Province, Grant/Award Number:
BK20200044; National Natural materials are usually bimetallic or polymetallic. These derivatives not only
Science Foundation of China, inherit the structural advantages of PB/PBAs, but also usually solve the
Grant/Award Number: U1904215; Open
problem of poor conductivity of PB/PBAs. Therefore, derived materials can
Fund of National Joint Engineering
Research Center for abrasion control and show more excellent electrochemical performance. In recent years, the
molding of metal materials, preparation and electrochemical application of hollow PB/PBAs and their
Grant/Award Number: HKDNM2019010;
Program for Young Changjiang Scholars
derivatives have attracted more and more attentions. In this article, the
of the Ministry of Education, China, synthesis strategies of hollow PB/PBAs and their derived materials are
Grant/Award Number: Q2018270; the systematically summarized. The applications of related materials in the field of
Fundamental Research Funds for
the Central Universities, electrochemistry are introduced in detail. And the prospects and challenges
Grant/Award Number: NS2021039 are further analyzed.
KEYWORDS
battery, electrocatalysis, electrochemistry, hollow structure, Prussian blue analogues,
supercapacitor
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2023 The Authors. Carbon Neutralization published by Wenzhou University and John Wiley & Sons Australia, Ltd.
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272 |
1 | INTRODUCTION treatment cause mass loss. In this process, the internal

precursor shrinks in volume and loses the organic part,
The excessive use of fossil energy has not only caused while the shell resists the volume shrinkage to maintain
energy crisis but also caused a series of environmental its original size. The cohesion and bonding forces
problems, such as the greenhouse effect caused by between the two phases interfaces play opposite roles,
carbon emission.[1–3] An effective way to solve these which facilitates the formation of controllable hollow
problems is to develop clean and abundant new energy, micron/nanostructures. The temperature, time and
such as solar, wind, tidal, and hydrogen energy, to heating rate are important affecting factors of heat
replace the traditional fossil energy.[4–6] Because of the treatment. Shen et al.[33] prepared NiCo2O4 with
high energy density and high reserves, hydrogen energy complex spherical hollow structure by thermal anneal-
has attracted extensive attention in many fields.[7,8] ing NiCo‐glycerate solid spheres in air. The ion
Water electrolysis is a promising way to obtain exchange process is an exchange process of anions or
hydrogen energy. To improve the efficiency of hydrogen cations between particles and solution, which is an
evolution reaction (HER)[9–11] and oxygen evolution effective way to build micron/nano hollow structures.
reaction (OER),[12–15] it is important to develop high‐ Shen et al.[34] successfully prepared a ball‐in‐ball hollow
efficiency catalysts. In addition to the research on the structure of ternary nickel cobalt sulfide by anion
access of new energy, efficient and advanced electro- exchange of nickel cobalt glycerate solid spheres. Based
chemical energy storage devices can ensure constant on previous reports, hollow materials with monolayer or
power output, so it also becomes an important part of multilayer shell structures can be synthesized by ion
energy development. exchange strategy.[35,36]
Reasonable structure design is of great significance to Prussian blue and its analogs (PB/PBAs) are a class of
improve the performance of materials. In recent years, coordination polymers with face‐centered cubic struc-
the design of micro/nanomaterials has attracted much ture, and the general formula is AxMA[MB(CN)6]y·zH2O.
attention.[16–18] Hollow nanomaterials have the advan- A is the metal cation embedded in the frame, and the
tages of large specific surface area, small density, and common ones are Na+ and K+. MA and MB are transition
abundant active sites.[19–21] Especially in the field of metal elements connected with cyano groups (MA = Mn,
electrochemistry, hollow materials usually show excel- Fe, Co, Ni, Cu, Zn, etc. and MB = Fe, Co, Cr, etc.).[37–39]
lent performance.[22,23] The formation mechanism of PB/PBAs are widely used in adsorption,[40] medicine,[41]
hollow structure mainly includes the template method, catalysis,[42] energy storage,[43] and so on. The derived
Kirkendall effect, thermal decomposition, and ion materials of PB/PBAs not only retain the variable
exchange.[24] The template method has a wide range of structure, adjustable composition, rich pore structure,
applications. Single/multilayer shell structures can be and other characteristics of PB/PBAs, but also improve
synthesized by the template method. Using carbonaceous the conductivity of PB/PBAs after the derivatization
microsphere as a template, Lai et al.[25] prepared process. This makes PB/PBAs derived materials usually
different multiple‐shell metal oxide hollow microspheres, exhibit excellent electrochemical performance. Gener-
such as α‐ Fe2O3, Co3O4, NiOCuO, etc. The template ally, PB/PBAs prepared by simple precipitation reactions
method includes the hard template method and the soft are solid structure,[44,45] which greatly hinders the
template method.[26,27] The process of forming a hollow exposure of active sites and increases the difficulty of
structure with the hard template method includes the mass transfer. The electrochemical properties of PB/
formation of outer shell on the surface of hard template PBAs and their derivatives can be improved via two
and the removal of hard template via suitable etching approaches. On one hand, composition adjustment
agent. The common soft templates mainly include improves electrochemical performance by adjusting the
emulsion droplets, vesicle/micelle and gas bubbles.[28] types of metal elements or introducing other non‐
Soft templates are generally removed by washing or metallic elements. For example, metal doping is a very
calcination. A hollow structure can also be synthesized effective modification strategy, which is based on the
according to the Kirkendall effect.[29–31] The formation synergistic effect between different transition metals. In
mechanism is based on the different diffusion rate of ions addition, transition metal phosphide,[46,47] transition
in the multi‐component system. The synthesis of cobalt metal sulfide[48,49] and transition metal oxide[50,51]
oxide and cobalt sulfide hollow nanocrystals based on the derived from PB/PBAs usually exhibit high performance.
Kirkendall effect was first reported in 2004.[32] The On the other hand, the design of morphology and
construction of hollow structure by thermal decomposi- structure is also very effective to improve the electro-
tion is to heat‐treat the sample at a certain temperature. chemical performance of PB/PBAs. The hollow
The removal of water and other gases during heat structure has advantages over the solid structure for
| 273
electrochemical applications.[52–55] In recent years, the Finally, the existing problems and development direc-
research of PB/PBAs with hollow structure has attracted tions are proposed.
more and more attention.
According to the morphology, the hollow structure
of PBAs can be approximately divided into three 2 | ELECTROCHEMICAL
categories: closed single‐shelled hollow structure, open APPLICATION
hollow structure, and hierarchical hollow structure
(Figure 1).[56] The synthesis method of single‐shelled 2.1 | Batteries
hollow structures is simple and the most common. The
open hollow structure generally refers to the polyhedral Traditional fossil fuels have been unable to meet the
cage or frame. Compared with closed single‐shelled increasing demand for energy and environmental protec-
hollow structures, the cage has more pores on the tion. It is urgent to develop new clean energy. Advanced
surface, while the frame structure only retains the edges electric energy storage equipment is very important
and corners in the geometric structure. For open hollow for the development and application of new clean
structure, the electrolyte can contact with the material energy.[57–60] Rechargeable batteries, such as lead‐acid
more fully, thus improving the reaction efficiency. batteries,[61] nickel‐metal hydride batteries,[62,63] and
Hierarchical hollow structures refer to hollow structure lithium‐ion batteries (LIBs),[64,65] have been widely used
with high complexity in cavity structure. The physical in many fields. The electrolyte has an important
and chemical properties of hierarchical hollow struc- influence on the performance of the battery.[66–69] The
tures can be improved greatly by reasonable structure organic electrolyte batteries have wider electrochemical
design and composition adjustment. The existence of window[70–72] and higher energy density.[73–75] However,
substructure can increase the exposed area of active organic electrolytes are volatile and toxic. Compared with
sites to a certain extent, thus improving the electro- organic electrolyte, the electrochemical window of
chemical activity. aqueous electrolyte is narrow. However, it has the
In this review, the structure design of hollow PB/ following features: 1) low cost, 2) safer and more
PBAs and the preparation of derivatives in recent years environmentally friendly than organic electrolyte, and
are classified and summarized, and the formation 3) the conductivity of ions in aqueous electrolyte is 2–3
process and related mechanism of hollow structure are orders of magnitude higher than that of organic
introduced in detail. In addition, the applications electrolyte, which ensures the good rate perform-
of hollow PB/PBAs and related derivatives in the field ance.[76–78] Therefore, aqueous batteries can play impor-
of electrochemistry are emphatically introduced. tant roles in some fields as well. In addition to the
FIGURE 1 Schematic illustration of various hollow structures of Prussian blue and its analogs (PB/PBAs).
274 |
influence of electrolyte, the electrode material is also an cathode material of lithium‐sulfur (Li‐S) battery
important factor to determine the battery performance. (1010.2 mA h g−1 at 0.5 C). Xu et al.[83] designed
PB/PBAs are a kind of ideal electrode materials with low highly‐crystallized and Na‐rich PBA (Na1.51Fe[Fe
cost, open frame structure, high theoretical capacity and (CN)6]0.87·1.83H2O) hollow nanospheres, which showed
good stability. The energy storage mechanism of PB/ high initial Coulombic efficiency and outstanding cyclic
PBAs is based on ion insertion and desertion and redox stability as the cathode material of sodium‐ion batteries
reaction of transition metals.[79–81] (SIBs). Chen et al.[84] synthesized a hollow bimetallic
PB/PBAs can be used as electrode materials for phosphating (Ni‐Fe‐P/NC) with double shell structure
various battery systems (Table 1). In addition to by phosphating NiFe PBA. When used as electrode
common univalent ions such as Li+, K+ and Na+, materials for potassium‐ion batteries (KIBs) and Li‐S
multivalent ions such as Zn2+, Mg2+ and Al3+ can also batteries, Ni‐Fe‐P/NC shows stable cycling and superior
be reversibly embedded and extracted in PBAs rate performance. At present, the research on PBAs as
(Figure 2).[91–93] Based on the current research, it can battery electrode materials has been quite extensive and
be found that when PBAs are used as electrode profound, and there are a lot of reviews specifically
materials of aqueous batteries, metal ions undergo a introducing the progress of PBAs applied to various
hydration process before entering PBAs and then batteries. Wang et al.[94] discussed the application of
dehydrate after entering PBAs. In an aqueous electro- PBAs in rechargeable batteries in detail and the
lyte, the radius of ions will become larger after classification of that according to the type of embedded
hydration, which puts forward higher requirements cations and transition metals. Zhou et al.[95] specifically
for the structural stability of PBAs. In addition, the described the progress of hexacyanoferrates‐type PBAs
interstitial water and vacancies in the PBAs structure as cathode materials for rechargeable sodium and
also impair the storage capacity of cations. Kang potassium ion batteries, in which the structure, redox
et al.[82] designed four hollow cubic materials using properties, and methods to improve electrochemical
Co‐Mn PBA as the precursor by changing the vulcan- properties of PBAs were analyzed. Xu et al.[96] discussed
ization temperature. Among all samples, the sample the progress of PBAs as electrode materials for aqueous
whose vulcanization temperature is 600°C (S@CoS1.097/ monovalent and multivalent ion batteries and seawater
MnS/NC@NC‐600) has the best performance as the desalination.
TABLE 1 Summary of PBA‐based electrode materials for rechargeable batteries.

Materials Applications Performance Electrolyte Ref.
−1
S@CoS1.097/MnS/NC@NC‐600 Li‐S battery 1010.2 mA h g at 0.5 C Li2S6 [82]
651.1 mA h g−1 after 200
cycles
Na1.51Fe[Fe(CN)6]0.87·1.83H2O SIB 124.2 mAh g−1at 17 mA g−1 1.0 M NaClO4 [83]
65.3% after 1000 cycles
Ni‐Fe‐P/NC KIB 172.9 mA h g−1 after 1600 3.0 M potassium bis [84]
cycles at 500 mA g−1 (fluorosulfonyl)imide
Hollow KxNayMnFe(CN)6 SIB 128 mA h−1 at 50 mA 83.6% 1.0 M NaClO4 [85]
after 2000 cycles
NiFe(II) PBA nanoframes SIB/LIB 1000 mA g−1 90% after 500 1.0 M NaClO4/1.0 M LiPF6 [86]
cycles/200 mA g−1
Cu‐CoSe2 NFCs NIB 470 mA h g−1 at 0.1 A g−1 0.1 M NaClO4 [87]
90% after 100 cycles
Hollow‐structures SIB 123.1 mA h g−1 at 0.1 A g−1 1.0 M NaClO4 [88]
CoFe‐PBA@PDA 71.5% after 500 cycles
CoMn‐PBA HSs AZIB 128.6 mA h g−1 at 0.05 A g−1 2.0 M Zn(CF3SO3)2 [89]
76.4% after 1000 cycles
Ag@Co3O4 HNB LIB 1015 mA h g−1 at 200 mA g−1 1.0 M LiPF6 [90]
Abbreviations: AZIB, aqueous Zn‐ion battery; KIB, potassium‐ion battery; LIB, lithium‐ion battery; LI‐S, lithium‐sulfur battery; PBA, Prussian blue analog;
SIB, sodium‐ion battery.
| 275
FIGURE 2 Schematic of ion insertion and extraction in Prussian blue analogs (PBAs).
2.2 | Supercapacitors combines the advantages of batteries and supercapaci-

tors to provide high power and energy density.
Supercapacitor is a new type of energy storage However, it is limited by the slow kinetics and poor
device.[97–100] Its output power density is hundreds or cycle life of battery electrode, which hinders its
thousands of times more than that of battery, and it can practical application. Hollow nanostructured electrode
quickly collect/release energy.[101–104] The high power materials can provide more abundant active sites and
density and fast energy storage benefit from the special shorten the ion transport distance, which is of benefit
charge storage mechanism.[105–107] The capacitance to enhancing the performance of supercapaci-
mainly comes from the surface effect or surface tors.[22,115,116] The poor conductivity of PBAs limits
reaction of the electrode material, including electro- their direct applications in supercapacitors. To solve
chemical adsorption and desorption of cations/anions this problem, PBAs can be combined with conductive
between electrode and electrolyte and Faradaic materials, such as graphene or conductive polymers, or
reaction on the surface of electrode.[108,109] There is be derived to form functional materials (Table 2).[44,125]
no diffusion process in the interior of the materials.
According to the charge storage mechanism, super-
capacitors can be mainly divided into three types: 2.3 | Electrocatalysis
electric double‐layer capacitors (EDLCs), pseudocapa-
citors and hybrid capacitors (HSC) (Figure 3).[110–112] Electrocatalytic water splitting is a process of converting
EDLCs store electrical energy in the form of static electric energy directly into chemical energy, which is an
electricity. When a voltage is applied, the electrostatic effective strategy for hydrogen production.[126–128] In the
charge accumulates on the surface of the electrode to process of water decomposition, HER occurs at the
form a double layer. Pseudopacitors are based on cathode to produce hydrogen, and oxygen evolution
reversible redox reactions between electrodes and reaction occurs at the anode to produce oxygen. HER is a
electrolytes. Pseudocapacitors generally exhibit greater two‐electron process, which involves the formation of
specific capacitance than EDLCs. When an electric H–H bond.[129,130] The OER process, including O–H
potential is applied, the electrolyte ions undergo a bond breakage and O–O bond formation, is a complex
reversible Faraday reaction to produce a redox pseu- multistep proton‐coupled electron transfer pro-
docapacitor. In addition, intercalation pseudocapaci- cess,[131,132] resulting in the slow kinetics of OER
tance and underpotential deposition are also the (Figure 4a). Therefore, the OER process requires a high
sources of pseudocapacitance. A typical HSC uses the overpotential, which limits the efficiency of water
battery electrode as the negative electrode to store decomposition and hinders the efficiency of H2 genera-
energy and the capacitor electrode as the positive tion. Therefore, the OER half‐reaction becomes a bottle-
electrode to release energy.[113,114] In theory, HSC neck reaction for electrocatalytic water splitting.[12,133]
276 |
F I G U R E 3 Ragone plot of different energy storage devices and schematic storage mechanisms of electric double‐layer capacitors
(EDLCs) and pseudocapacitors. Reproduced with permission: Copyright 2020, Wiley‐VCH.[110]
TABLE 2 Summary of PBA‐based electrode materials for supercapacitors.

Materials Specific capacitance Retention Type Electrolyte Ref.
−1
CoHCF 292 F g 93.1% after 8000 cycles Hybrid capacitor 0.5 M Na2SO4 [117]
−1 −1
NiCoP‐4‐500 1590 F g at 1 A g 78.2% after 12,000 cycles Hybrid capacitor 6 M KOH [118]
CuO/Co3O4 181.8 F g−1 73.68% after 6000 cycles Asymmetric supercapacitor 3 M KOH [119]
H‐MnO2‐TEA 316.8 F g−1 at 0.5 A g−1 96.1% after 10,000 cycles Pseudocapacitor 1 M Na2SO4 [120]
−1 −1
HMFO‐CSN 894 C g at 1 A g 90.5% after 10,000 cycles Hybrid capacitor 6 M KOH [121]
−1 −1
NiS nanoframes (300 nm) 2112 F g at 1 A g 91.8% after 4000 cycles / 6 M KOH [122]
−1 −1
CoSe2/FeSe2 HNCs 1197.90 C g at 1 A g 91.47% after 10,000 cycles Hybrid capacitor 6 M KOH [123]
−1 −1
NiF2/CoF2 1491 F g at 1 A g 78.7% after 3000 cycles Pseudocapacitor 2 M KOH [124]
Abbreviation: PBA, Prussian blue analog.
| 277
The reaction equations for HER and OER reactions in the efficiency of water splitting and hydrogen production.
acid or alkaline electrolytes are different (as shown in At present, most of the common electrocatalysts are
Figure 4b). precious metal based catalysts, such as Pt,[139] Ir[140] and
The activity of HER in alkaline solution is lower than Ru.[141] Although these catalysts have high efficiency and
that of 2–3 orders of magnitude in acidic solution. Studies excellent stability, they are limited by low reserves
have shown that the activity of HER in acidic medium is and high cost. Therefore, it is urgent to develop low‐cost
related to hydrogen adsorption.[134,135] In alkaline and efficient electrocatalysts. PB/PBAs is a promising
medium, hydrogen adsorption, hydroxyl adsorption and electrocatalyst with simple synthesis method, adjustable
water dissociation are all important influencing fac- active site, and uniform distributed catalytic sites.
tors.[136,137] For OER reactions in alkaline medium, the Moreover, due to the structure and composition char-
stronger covalent bonds in H─O─H must be broken, acteristics of PB/PBAs, their corresponding derivatives,
rather than weaker covalent bonds in H3O+.[138] The such as metal phosphide,[142] metal oxide,[143] metal
electrocatalyst with high activity and high efficiency can sulfide,[144] etc., have the advantages of adjustable
reduce the activation energy of the reaction and improve composition, uniform distribution of active sites, large
F I G U R E 4 (a) The oxygen evolution reaction (OER) mechanism for alkaline conditions. (b) Schematic of the hydrogen evolution
reaction (HER) and OER in acidic and alkaline solutions.
TABLE 3 Summary of PBA‐based electrode materials for OER/HER.

Materials Applications j (mA cm−2) η (mV) Electrolyte Ref.
Co‐Fe‐O frames OER 10 290 mV 1.0 M KOH [145]
Mn2Co2C (PBA‐Ⅲ−700) ORR / / 0.1 M KOH [146]
Co‐Fe hollow cage OER 10 330 1.0 M KOH [147]
Ni‐Fe‐Se cage OER 100 270 1.0 M KOH [148]
Ni‐Co mixed oxide OER 10 380 1.0 M KOH [149]
Pd‐e‐NiCo‐PBA‐C HER/OER 10 47/55 0.5 M H2SO4 [150]
147/67 1.0 M KOH
Co3O4/Co‐Fe oxide double‐shelled nanoboxes OER 10 297 1.0 M KOH [151]
Co‐P@IC/(Co‐Fe) P@CC nanoboxes HER/OER 10 53/174 1.0 M KOH [152]
Fe‐CoP HTPAs HER/OER 10 98/230 1.0 M KOH [153]
Fe‐CoxP OER 10 300 1.0 M KOH [154]
NiCoFe‐P‐NP@NiCoFe‐PBA OER 10 223 1.0 M KOH [155]
NiCoFeP‐HN OER 10 294 1.0 M KOH [156]
Co3S4@MoS2 HER/OER 10 136/280 1.0 M KOH [157]
Se‐(CoFe)S2 nanobox OER 10 281 1.0 M KOH [158]
Fe‐Co‐F‐400 OER 10 250 1.0 M KOH [159]
Abbreviations: HER, hydrogen evolution reaction; OER, oxygen evolution reaction; PBA, Prussian blue analog.
278 |
specific surface area, etc., showing excellent electrocata- of metal ions and organic ligands. Because of the
lytic water splitting performance (Table 3). hydrophilic property of cyanide precursor, the hollow
structure can be constructed by selecting suitable
surfactant. In recent years, many works about the
3 | SYNTHES IS STR ATEGY O F regulation of hollow PB/PBAs by surfactants articles
HOLLOW PB/PBAS have been reported. According to the reported works,
sodium citrate, polyvinylpyrrolidone (PVP), sodium
3.1 | Surfactant regulation dodecyl sulfate (SDS), etc., can be used to assist the
synthesis of hollow PB/PBAs.[167,168]
Surfactants are organic compounds with both water‐ Nai et al.[145] successfully prepared three kinds of
soluble hydrophilic groups and oil‐soluble hydrophobic hollow Co‐Fe PBA with special morphology by adjusting
groups.[25,160] Surfactants can be classified into ionic and the concentration of PVP and citrate, namely Co‐Fe PBA
nonionic surfactants,[161,162] and ionic surfactants are cages, Co‐Fe PBA frames and Co‐Fe PBA boxes
divided into anionic and cationic surfactants.[163,164] (Figure 5a,b). In the reaction process, the Co‐Fe PBA
Based on the amphiphilic feature of surfactants, they cubes are formed quickly in a very short time and serves
can be assembled into different micelles in solution. as the template for subsequent reactions. The role of PVP
These micelles can be used as templates or structure‐ and citrate is to improve the stability of the (100) and
directing agents to control the size, morphology, and (111) crystal planes in Co‐Fe PBA. The newly generated
pore size and distribution of nanomaterials. Based on the Co‐Fe PBA will preferentially deposit on the edges and
Janus characteristics[165,166] of hydrophilic and hydro- corners of the cube with relatively high reactivity, and
phobic groups, surfactants can also increase the solubility the presence of PVP makes the Co‐Fe PBA deposit on
F I G U R E 5 (a) Schematic illustration of the construction of different Co‐Fe PBA hollow structures by a self‐Templated epitaxial growth
strategy. (b) Field emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of Co‐Fe
PBA boxes cages and frames. Reproduced with permission: Copyright 2018, Elsevier.[145] (c) SEM and TEM images of H‐KMF.
(d) Charge‐discharge curves and cycle performance of H‐KMF electrode measured at low current density of 50 mA g−1. Reproduced with
permission: Copyright 2020, Elsevier.[85] (e) Schematic illustration of the nanostructural evolution from PBA‐I to PBA‐IV. (f) TEM
images of PBA‐Ⅰ, PBA‐Ⅱ, PBA‐Ⅲ, and PBA‐Ⅳ. (g) The surface energies of the crystal planes of MnCoPBA. Reproduced with permission:
Copyright 2020, Wiley‐VCH.[146] PBA, Prussian blue analog.
| 279
each surface of the cube to form surface‐closed boxes. thermodynamics during the morphology change of
High concentration of citrate results in the truncation of MnCoPBA were analyzed in detail. As shown in
surface‐closed boxes, while low concentration of citrate Figure 5g, the surface energy of (111), (110) and (100)
results in angular etching and open cage structure. This in MnCoPBA were −59.4 J cm−2, −14.2 J cm−2 and
is because the Co‐Fe PBA cube generated at the −9.3 J cm−2, respectively. In the initial stage of crystal
beginning forms quickly and has many defects, so its formation, reaction kinetics is the main factor affecting the
thermodynamic stability is very poor. Meanwhile, the crystal morphology. Because the surface energy of (111) is
outer shell structure generated later is relatively stable, larger, ions in the solution are more inclined to adsorb on
which results in a gradual dissolution of the interior it. Therefore, the growth rate of (111) surface is relatively
during the reaction and the formation of hollow fast and more (111) surfaces are exposed. So, the six
structure. The Co‐Fe mixed oxides with different truncated faces in PBA‐Ⅰ belong to the (100) faces. SDS is an
structures were obtained by heat treatment of precursor ionic surfactant, which tends to adsorb on the (111) faces
with different structures, and the framework showed the with higher surface energy, and this will inhibit the
best electrocatalytic performance. Mn‐base Prussian blue degradation of (111) face and the growth of (100) face. In
analogue, which possesses high theoretical capacity, has addition, the adsorption probability of ions on (111) face
been considered as a promising cathode material for decreases with the increase of the number of crystal nuclei.
sodium‐ion batteries. However, the problems of struc- Taking all these factors into consideration, the growth rate
tural instability and poor cycling performance have difference between (111) and (100) will gradually decrease,
limited its application. Jiang et al.[85] prepared a hollow and the crystal size will become more uniform. In addition,
Mn‐based Prussian blue analogues KxNayMnFe(CN)6 the thermodynamics is also an important factor affecting
(H‐KMF) with the help of sodium citrate (Figure 5c). crystal growth. The surface energy of (111) face is higher, so
The sample exhibited a specific capacity of 128 mA h g−1 it is more unstable and will be completely dissolved during
as the electrode material of sodium‐ion battery the reaction process. This results in the etching of the (111)
(Figure 5d). The effect of sodium citrate in the reaction face, and thus PBA‐Ⅱ exhibits this special structure. The
process was analyzed by comparing the difference reason for the formation of PBA‐Ⅲ is that the dissolution
between the product with sodium citrate and the product rate of (111) face is higher than the crystallization rate.
without sodium citrate (KMF). First, sodium citrate in While the law of (100) face is opposite. This causes the shell
solution adsorbs Mn2+ through the electrostatic interac- grows outwards along the (100) face until it forms a sealed
tion, and the competition between ferricyanide and cube, while the interior continues to dissolve along the
sodium citrate will reduce the formation rate of KMF eight corners. At the last stage of the reaction, the initial
nanoparticles, thus forming a regular cubic structure. part growing along the (111) face completely dissolves
The remaining citrate in the solution adsorbs to the because of the too fast growth rate and poor thermal
surface of the KMF, which prevents the particles from stability, and finally forms a cuboidal shell with open cross
growing further into the cavity. Besides assisting faces. The morphology of MnCoPBA is closely related to
construction of hollow structures, the addition of sodium surfactant and reaction time.
citrate also slows down the formation rate of PBAs, thus
reducing vacancies in the structure. The hollow structure
not only alleviates the problem of volume change during 3.2 | Chemical etching
charging and discharging, but also shortens the diffusion
distance of sodium ions. The synergistic interaction Chemical etching is an effective method to construct
between different kinds of alkali metals in the composi- hollow structures.[169,170] Similar to the process of removing
tion will further improve its structural stability. template in hard template method, the hollow structure is
Wang et al.[146] reported the preparation of MnCoPBA created by etching the core of the solid template. The
with four different morphologies (PBA‐Ⅰ, PBA‐Ⅱ, PBA‐Ⅲ, precursors used for etching are usually isomorphic for
and PBA‐Ⅳ) via adjusting reaction times by adding SDS interior and exterior. Therefore, creating differences in
(Figure 5e). The morphology of MnCoPBA in different solubility or chemical stability between the interior and
reaction stages can be observed by TEM (Figure 5f). PBA‐Ⅰ exterior is the key to chemical etching method.
is a solid structure. PBA‐Ⅱ looks like a cross from three
angles. PBA‐Ⅲ exhibits a hollow core‐shell structure. The
core is a cube whose corners are etched, and the exterior is 3.2.1 | Acid etching
a thin cubic shell. PBA‐Ⅳ is a hollow cube whose six faces
are etched into the cross shape, and the core completely The acid etching strategy is very effective for the
disappears. In this work, the reaction kinetics and preparation of hollow PB/PBAs. Hu et al.[171] treated
280 |
F I G U R E 6 (a, b) TEM images of solid PB mesocrystals and hollow PB mesocrystals (average particle size: 110 nm), and the
corresponding selected‐area electron diffraction (ED) patterns of one particle. Reproduced with permission: Copyright 2012, Wiley‐VCH.[45]
(c) Schematic illustration showing the structure evolution of NiFe(II) PBA cubes, NiFe(II) PBA concave cubes, and NiFe(II) PBA
nanoframes. (d–f) TEM images of NiFe(II) PBA cubes, NiFe(II) PBA concave cubes, and NiFe(II) PBA nanoframes. (g–i) Wide‐angle XRD
patterns of: NiFe(II) PBA cubes, NiFe(II) PBA concave cubes, and NiFe(II) PBA nanoframes. (j) Cycling performance of PBA as a
cathode for a sodium ion battery at a current rate of 100 mA g−1. Reproduced with permission: Copyright 2016, Wiley‐VCH.[46]
PBA, Prussian blue analog; TEM, transmission electron microscopy.
solid PB cube with uniform morphology and size in 1.0 M material during the reaction (Figure 6g–i). XRD analysis
HCL at 140°C for 4 h, and a cavity was formed in the shows that the initial NiFe(Ⅱ) PBA is rhombohedral
solid structure (Figure 6a,b). Zhang et al.[86] used an structure, and the final nanoframe is face‐centered‐cubic
organic‐free preferential etching strategy to develop a structure. In addition to the change of crystal structure,
synthesis method of hollow single‐crystal PBA nano- the elemental composition also changes during etching.
frames by taking advantage of the heterogeneous The ratio of Fe: Ni decreased gradually, which may be
distribution of defects in PBA crystals (Figure 6c). due to the gradual dissolution of [Fe(CN)6]4− during the
Although the etching method with organic acids has formation of the nanoframes. HCL destroys the coordi-
been widely used, organic molecules are easily trapped in nation bonds in the PBA structure, and the middle part
the pores of the structure, which has a negative effect on of the outer surface of the cube can be dissolved more
the electrical energy storage performance. By observing quickly, finally obtaining this special nano‐frame struc-
the morphologies of NiFe(Ⅱ) PBA in HCL at different ture. The results of sodium ion battery test show that the
times, after 5 min, NiFe(Ⅱ) PBA has no obvious size electrochemical performance of the nanoframes is better
change, but the originally smooth surface of PBA than that of the initial NiFe(Ⅱ) PBA, exhibiting better rate
becomes concave due to slight etching (Figure 6d,e). performance and cycle stability (Figure 6j). It is worth
The electron diffraction (ED) results of the concave cubes noting that, although the acid etching synthesis strategy
and the initial cubes are similar, which indicates that is simple and effective, the cyanogen in Prussian blue
they have similar single crystal structure. When the and its analogues is very easy to react in hot acidic
treatment time reaches 1 h, a special frame structure can solution to produce hydrogen cyanide gas. Therefore, the
be observed (Figure 6f), and the size of the frame is experimental process must be carried out in a fume hood,
consistent with that of NiFe(Ⅱ) PBA. It is worth noting and the corresponding protection should be done.
that similar ED results were obtained for the retained In addition to the direct use of strong acids for
nano‐frame structure, but the crystal structure was etching, Feng et al.[147] prepared CoFe PBA and NiFe
different from the initial one. X‐ray diffraction (XRD) PBA hollow cages (CFHC and NFHC) by simple ethanol
result reveals the changes in the crystal structure of the solvothermal treatment. The relationship between the
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formation of hollow structures and the reaction time can Cu‐doped CoSe2 nanoframe cubics (Cu‐CoSe2 NFCs)
be observed from the TEM images of different reaction structures using a similar process (Figure 7c). First,
times. First, hollow structure is created diagonally, then the Co‐Co PBA was etched into hollow structure
widened and deepened until the center is completely (Figure 7d,c), and then it was selenized. Finally, the
etched. In addition to the effect of reaction time, the cation exchange strategy was used to obtain Cu‐CoSe2
experimental results also confirm that the reaction NFCs.
temperature and the protective effect of PVP also affect In addition to selenides, other hollow transition metal
the formation of hollow structure. If the reaction tempera- derivatives were also prepared based on the precursor
ture is too low, the formation process of hollow nanocages with special open structure. For example, Han et al.[149]
will slow down. If the reaction temperature is too high, the synthesized a Ni‐Co mixed bimetallic oxide nanocage.
etching reaction will be too severe and the structure will be Ni‐Co PBA cube obtained by precipitation method was
damaged seriously. The reaction mechanism of cavity transformed into Ni‐Co PBA cage under the etching of
formation was further explained by the change of pH value ammonia. Then, Ni‐Co mixed oxide cage with strong
before and after the solvothermal reaction. The pH value of electrocatalytic activity and good stability was obtained
the system changed from 8.12 to 11.20 before and after the by annealing Ni‐Co PBA cage in air. This work also
reaction. The significant increase of pH value indicates that explores the evolution process from cubic structure to
protons are constantly consumed during the solvothermal nanocages, and the conclusion is basically consistent
reaction process, and protons originate from the continuous with the above work. That is, etching occurs first at the
ionization of ethanol (CH3CH2OH → CH3CH2O− + H+). corner and then along the diagonal direction of the cube
The reaction mechanism of ethanol solvothermal etching is (Figure 7f,g). It is also mentioned that the etching
similar to that of HCL etching. However, under the action reaction can be slowed down by reducing the amount of
of this very weak acid, the protons in situ released by ammonia. In addition, the authors proposed that the rate
ethanol are dispersed into the cube structure along the of etching reaction depends on the defect density of the
nanopore channel driven by the concentration gradient, region, and a series of experiments were conducted to
and the etching reaction is gradually extended along the prove this. First, the 1 day and 7 days aged PBA cubes
diagonal. were etched with ammonia, and the 1‐day aged Ni‐Co
PBA had more observable defects than the 7‐day aged Ni‐
Co PBA. When the two precursors were treated under
3.2.2 | Ammonia etching the same etching conditions, the samples with many
defects collapsed into plate‐like etching products due to
In addition to the acid etching, hollow PB/PBAs can also the faster etching rate. Moreover, Ni‐Co PBA was
be prepared under alkaline conditions. Anisotropic annealed directly in air, and it was found that the
etching of ammonia can produce PBAs with unique internal pores were still along the diagonal direction of
open structure. When using ammonia to etch solid PBA the cube. This result confirmed that, in the process of
cube, the etch first occurs at the position of the corners PBA formation, dissolution and recrystallization were
and then continues along the diagonal direction. Nai more likely to occur on the outside, which leaded to the
et al.[148] used ammonia etching strategy to prepare Ni‐Fe internal structure looser than the external structure.
PBA open nanocages and derived the precursor into Ni‐ Therefore, the external structure can be well preserved
Fe mixed diselenide nanocages (Ni‐Fe‐Se cages). OER after the etching reaction. Zhang et al.[150] also used the
test results show that the Ni‐Fe‐Se cages have the same ammonia‐assisted strategy to prepare NiCo‐PBA‐C
smallest overpotential among all samples. The outstand- nanocages. It shows a relatively excellent catalytic
ing catalytic performance is closely related to the performance (Figure 7h–j).
composition and structure. The structural changes
during the process of ammonia etching were also
characterized. Because of the different reactivity on the 3.3 | Ion exchange
surface of the cubic structure, the etching of ammonia
first occurs at the corner of the cube structure with Based on the chemical instability of metal‐organic frame-
relatively high surface energy, and the etching will works (MOFs), ion‐exchange reaction can realize the
continue gradually along the diagonal direction of the transformation of simple structure of MOFs precursors into
cubic structure with the increase of reaction time. As the complex structures. Therefore, ion‐exchange approach is an
etching depth increases continually, the cavity gets wider effective strategy for the structural design and composition
and wider, until it cuts through the whole cube transformation of nanomaterials.[172,173] Compared with
(Figure 7a,b). In addition, Zhang et al.[87] prepared acid or alkali etching methods to prepare hollow PB/PBAs,
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F I G U R E 7 (a) The corresponding schematics illustrate the structural evolution of the exterior and interior of the Ni‐Fe PBA nanocubes
to form nanocages. (b) FESEM and TEM images of the products obtained in the etching procedure for the fabrication of the Ni‐Fe PBA
nanocages at 0 min, 1 min, 3 min, and 5 min. Reproduced with permission: Copyright 2017, Wiley‐VCH.[148] (c) Schematic diagram of
synthesis of Cu‐CoSe2 NFCs by etching and ion exchange reaction. (d, e) SEM images of Co‐Co PBA and Co‐Co PBA NFCs. Reproduced
with permission: Copyright 2021, Elsevier.[87] (f ) The corresponding schematics illustrate the formation process of the Ni‐Co PBA cages. (g)
TEM images of the etching products obtained after reacting 20 mg of Ni‐Co PBA cubes with 2.5 mL of ammonia at room temperature for 0 h,
0.5 h, 2 h, and 6 h. Reproduced with permission: Copyright 2016, Wiley‐VCH.[149] (h) Schematic diagram of the synthesis of e‐NiCo‐PBA‐C.
(i, j) SEM images of NiCo‐PBA and e‐NiCo‐PBA. Reproduced with permission: Copyright 2020, Wiley‐VCH.[150] NFCs, nanoframe cubics;
PBA, Prussian blue analog; SEM, scanning electron microscopy; TEM, transmission electron microscopy.
the ion exchange strategy is much safer. Moreover, the hollow PBAs. The process of anion exchange not only
gradual reaction can avoid the structural damage that is enables the transition from solid structure to hollow
caused by the rapid dissolution of the template. The structure, but is usually accompanied by the doping of new
resulting PBAs tends to crystallize better as well.[174] metal elements. The synergistic effect of different metals
often plays a positive role in the electrochemical perform-
ance. Wang et al.[151] synthesized the ZIF‐67/Co‐Fe PBA
3.3.1 | Anion exchange yolk‐shell nanoboxes (YSNCs) using solid cubic ZIF‐67 as
the precursor by anion exchange reaction. The precursor
Using zeolite imidazolate framework (ZIF) as the template was further annealed to obtain a Co3O4/Co‐Fe oxide
for anion exchange, hollow PBAs can be obtained by double‐shelled nanoboxes (DSNBs) (Figure 8a). In addi-
retaining PB/PBAs layer. ZIF‐67 is a very representative tion, if a small amount of acetic acid is introduced, the
zeolite imidazolate, which is often used as a precursor for internal ZIF‐67 can be completely etched to obtain Co‐Fe
the construction of hollow Co‐based PBA. When dispersed PBA single‐shelled nanoboxes (SSNBs) (Figure 8b,c). Zhu
in water, ZIF‐67 precursor hydrolyzes slowly and releases et al.[152] also used the cubic structure of ZIF‐67 as the
cobalt ions. When potassium ferricyanide or other similar precursor to prepare hollow PBA (Figure 8d–f). Different
substances are added to the precursor, ZIF‐67 is gradually from the previous anion exchange strategy, both K3[Co
etched, resulting in core‐shell ZIF‐67@PBA complexes or (CN)6] and K3[Fe(CN)6] were used as the anion sources in
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F I G U R E 8 (a) Schematic illustration of the formation process of Co3O4/Co‐Fe oxide DSNBs: (I) ion‐exchange reaction between ZIF‐67
NCs and [Fe(CN)6]3− ions to form ZIF‐67/Co‐Fe PBA YSNCs and (II) subsequent conversion to the Co3O4/Co‐Fe oxide DSNBs by thermal
annealing. (b, c) TEM images of ZIF‐67 NCs and Co‐Fe PBA SSNBs. Reproduced with permission: Copyright 2018, Wiley‐VCH.[151] (d)
Schematic illustration of the construction of Co‐P@IC/(Co‐Fe)P@CC electrocatalyst. (e, f) SEM and TEM images of ZIF‐67@Co‐Co/Fe PBA
hollow nanocubes. Reproduced with permission: Copyright 2020, Elsevier.[152] (g) Schematic illustration of the construction of mesoporous
Fe–CoP HTPAs. (h) SEM images of CoFe‐PBA HTPAs. Reproduced with permission: Copyright 2018, Wiley‐VCH.[153] (i) Schematic
representation of the formation mechanism. (j, k) TEM images of ZIF‐67 precursor and hollow‐structured CoFe‐PBA. Reproduced with
permission: Copyright 2021, American Chemical Society.[88] PBA, Prussian blue analog; SEM, scanning electron microscopy; TEM,
transmission electron microscopy.
this work. ZIF‐67@Co‐Co/Fe PBA hollow nanocubes were Furthermore, the Co‐P and Fe‐P produced in the subse-
obtained after seven days ageing. On this basis, hybrid quent phosphorization treatment can adjust the electronic
metal phosphide hollow nanocubes were designed (Co‐ structures and significantly reduce the adsorption‐free
P@IC/(Co‐Fe)P@CC). Based on the controllable assembly energies of the intermediate, which is beneficial to improve
and cooperative catalysis strategy, mixed metal phosphate the catalytic performance for HER. Moreover, the hollow
showed excellent OER and HER catalytic activities, with structure has been proved to increase the electrochemical
an overpotential of 174 mV (OER) and 53 mV (HER) at a active surface area. In addition to the usual cubic structure,
current density of 10 mA cm−2, respectively. The Co and Hu et al.[153] designed an Fe‐doped CoP hollow triangle
Fe introduced in the anion exchange process have the plate arrays. Using ZIF‐67 triangular plate arrays (ZIF‐67
synergistic effect to improve the catalytic activity of OER. TPAs) as templates, CoFe‐PBA hollow triangular plate
284 |
arrays (CoFe‐PBA HTPAs) were obtained by anion dodecahedron ZIF‐67 (Figure 8j). The gradual etching
exchange strategy. Fe‐CoP HTPAs were obtained after process avoids the rapid dissolution of the precursor and
phosphating (Figure 8g,h). The material has abundant the damage of the product structure, and finally obtains
active sites, short ion transport paths, and good hydrogen the complete hollow CoFe‐PBA (Figure 8k). To further
adsorption free energy. The electrochemical test results improve the structural stability of hollow CoFe‐PBA and
showed that the OER and HER overpotentials of the alleviate the negative effect of charging and discharging
material were 230 mV and 98 mV, respectively, at a current process on the material structure, a thin polydopamine
density of 10 mA cm−2. The overpotential is about 60 mV (PDA) was coated on the surface of CoFe‐PBA. Electro-
smaller than that of CoP TPAs, which fully indicates that chemical test results show that CoFe‐PBA@PDA not
ion doping and hollow structure have a positive effect on only exhibits excellent cycle stability and good rate
the electrocatalytic performance. performance, but also has a high Coulombic efficiency of
The 3D frame structure of PB/PBAs is very important about 100%.
for the research and development of battery materials. For the preparation of hollow PBAs by anion exchange
Hollow structure can not only alleviate the problem of method, in addition to ZIF‐67 as the template, glycerate
material volume change during the charging/discharging nanospheres are often selected as self‐sacrificial templates.
process, but also effectively shorten the ion transport Glycerate nanospheres can be obtained by solvothermal
path. Therefore, hollow PBAs have certain application reaction at high temperature with metal source, isopropa-
prospects in energy storage. Huang et al.[88] studied nol, and glycerol as reactants. Metal glycerate spheres are
hollow CoFe‐PBA obtained by anion exchange synthesis soluble in water, and metal ions will be slowly released.
strategy as the electrode material of sodium‐ion batteries Free metal ions can coordinate with anion groups, such as
(Figure 8i). Hollow CoFe‐PBA was prepared by adding [Fe(CN)6]3−, to form PBAs precipitation. With the continu-
[Fe(CN)6]4− to the aqueous solution of rhomb ous generation of PBAs, the solid structure will gradually
F I G U R E 9 (a) Schematic illustration of the construction of Fe‐CoxP hollow nanospheres. (b, c) SEM and TEM images of Co‐glycerate.
(d, e) SEM and TEM images of CoFe PBA. Reproduced with permission: Copyright 2020, Elsevier.[154] (f) The synthetic process of CoMn‐
PBA HSs. (g, h) SEM and TEM images of CoMn‐glycerate SSs. (i, j) FESEM and TEM images of CoMn‐PBA HSs. (k) XRD patterns of CoMn‐
glycerate SSs and CoMn‐PBA HSs. (l) Charge‐discharge voltage profiles at a current density of 0.05 A g−1 of CoMn‐PBA HSs, Mn‐PBA HSs
and Co‐PBA HSs electrodes. Reproduced with permission: Copyright 2021, Wiley‐VCH.[89] PBA, Prussian blue analog; SEM, scanning
electron microscopy; TEM, transmission electron microscopy.
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become hollow structure. Song et al.[154] prepared CoFe 3.3.2 | Cation exchange
PBA hollow spheres with a shell thickness of about 100 nm
by anion exchange reaction with K3[Fe(CN)6] using Co‐ The cation exchange strategy, which is based on the
glycerate spheres as sacrificial templates at room tempera- difference of solubility product constants, is also an
ture. Then, Fe‐CoxP hollow spheres were obtained by effective method for the preparation of hollow PB/PBAs.
phosphating (Figure 9a). SEM characterization results Under suitable reaction conditions, the substance with
(Figure 9b) show the surface changes of the material higher solubility product constant will be transformed
during the anion exchange process. After 10 min, the into a substance with lower solubility product constant.
smooth surface of the original sphere began to become Wang et al.[117] chose manganese hexacyanoferrate
rough, and with the extension of the reaction time, more (MnHCF) submicrocubes as the sacrificial template
and more nanoparticles deposited on the surface. Rough (Figure 10a). The solubility product constant of MnHCF
CoFe PBA nanoparticles can be easily observed in the SEM (Ksp = 1.9 × 10−3) is much higher than those of other
images of sample with a reaction time of 6 h (Figure 9d). PBAs. Because the MnHCF is unstable in water, the
TEM results (Figure 9c,e) reveal the transformation cation exchange reaction is easier to take place. MnHCF
process from solid structure to hollow structure. By submicrocubes was synthesized by the coordination
comparing the X‐ray photoelectron spectroscopy (XPS) precipitation method. Then, MnHCF and Co2+ were
results of cobalt in CoxP and Fe‐CoxP, it can be found that mixed in water. Cobalt Hexacyanoferrate (CoHCF)
the doping of Fe element reduces the peak position of Co hollow submicroboxes was obtained after 12 h at room
2p by 0.3 eV. This proves that there is an electronic temperature. TEM images (Figure 10b–d) show that the
coupling between Co and Fe in Fe‐CoxP. OER test results exchange process between Mn2+ and Co2+ is gradual,
shows that Fe‐CoxP has the highest catalytic activity because MnHCF gradually dissociates Mn2+ and
among all samples, which can be attributed to the [Fe(CN)6]2− in aqueous solution at a slow rate. In
synergistic effect between different metal elements and addition, because the solubility product constant of
the unique hollow nanostructure. Zeng et al.[89] designed CoHCF is low (Ksp = 6.7 × 10−22), the dissociated [Fe
Co‐substituted Mn‐rich PBA hollow spheres (CoMn‐PBA (CN)6]2− will coordinate with the added Co2+ to form a
HSs) (Figure 9f). CoMn‐PBA was obtained by one‐step CoHCF precipitate. CoHCF is continuously deposited
anion exchange reaction using CoMn glycerate spheres as on the surface of MnHCF with increasing reaction time.
templates. Mn‐PBA is an ideal cathode material for Therefore, MnHCF/CoHCF intermediates can be col-
aqueous Zn‐ion batteries (AZIBs) because of its high lected during the evolution process. When all MnHCF
theoretical capacity and output voltage. However, it has dissociates, there are only CoHCF hollow submicro-
poor cyclic stability because of the Jahn‐Taller distortion boxes. The specific capacity of the CoHCF submicro-
during the process of ion insertion and extraction. Metal boxes can reach 292 F g−1 for supercapacitor testing in
doping and structure design have been proved to alleviate Na2SO4 aqueous electrolyte (Figure 10e). In addition,
the problem of poor cycle life of Mn‐PBA. Co doping into this strategy of preparing hollow PBAs submicroboxes
Mn‐PBA can inhibit the Jahn‐taller distortion caused by without surfactant and etching agent can also be
Mn3+, and hollow structure can alleviate the volume extended to the synthesis of other PBAs, such as
change during charge‐discharge process. Through the CuHCF.
structural characterization results before and after the ion Similarly, Qiu et al.[175] obtained MnHCF by co‐
exchange reaction (Figure 9g‐i), it can be observed that the precipitation method, and then synthesized hollow
originally smooth solid sphere becomes a spherical shell of CoHCF by cation exchange strategy (Figure 10g). It is
about 200 nm composed of nanocube subunits. By worth noting that the difference in solubility of
comparing the XRD results (Figure 9k), it can be seen K3[Fe(CN)6] in water and ethanol are used to regulate
that the phase after the reaction corresponds to the the structure of CoHCF. Through the morphological
standard card of KMnFe(CN)6·nH2O. The inductively characterization results (Figure 10f), the surface of CoHCF
coupled plasma atomic emission spectroscopy (ICP‐AES) with ethanol participation has obvious pores. This
and energy‐dispersive X‐ray (EDX) results show that the phenomenon is probably caused by the formation of
final product contains Co element. According to the mesoporous structure during the process of ethanol
electrochemical test results (Figure 9l), CoMn‐PBA has spillage. With the increase of the reaction temperature,
high reversible capacity and favorable rate performance, the pore becomes larger and larger due to the continuous
and the capacity retention rate can reach 76.4% after more volatilization of ethanol. Ethanol in the solvent will not
than 1000 cycles. The capacity of CoMn‐PBA hollow only affect the pore structure, but also affect the size of the
spheres is significantly higher than that of Co‐PBA and product. With the increase of ethanol volume, the size of
Mn‐PBA. the product will gradually decrease, because the growth
286 |
F I G U R E 10 (a) Schematic illustration of the formation mechanism of CoHCF submicrobox. TEM images of CoHCF products collected
at different time (b) 0 h, (c) 0.5 h and (d) 6 h. (e) Charge/discharge curves of the CoHCF at different current density. Reproduced with
permission: Copyright 2017, Elsevier.[117] (f) TEM images of CoHCF‐0, CoHCF‐1, CoHCF‐2 and CoHCF‐3. (g) Schematic illustration
synthetic process for CoHCF. (h) XRD patterns of CoHCF. Reproduced with permission: Copyright 2021, Elsevier.[175] TEM, transmission
electron microscopy.
rate of PBAs crystal is closely related to the solubility of should also be further explored, which can also provide
K3[Fe(CN)6]. XRD results show the changes of material more possibilities for the design of PBAs derived
composition before and after cation exchange (Figure 10h). materials.
In this part, the synthesis strategies of hollow PB/
PBAs are summarized, including surfactant regulation,
chemical etching, ion exchange, etc. The structure 4 | HOLLOW PRUSSIAN BLUE
design of hollow PB/PBAs is very significant, because DERIVATIVE
hollow structure is positive for the improvement of
electrochemical performance. There are still some Although PB/PBAs have been extensively studied in the
problems in the structural design of hollow PBAs. First, field of electrochemistry, their application is largely
the reported structures of the hollow PBAs are mostly limited by their poor electrical conductivity.[176] There
simple hollow nanocubes. More other structures, such are many kinds of PB/PBAs derivatives and the prepara-
as hierarchical hollow structure and other complex tion method is simple. By using one‐step or multistep
structure, should be designed. This will bring more heat treatment, polymetallic components of phosphide,
possibilities for the improvement of electrochemical oxide, sulfide, alloy, etc. can be obtained. PB/PBAs
performance. In addition, PB/PBAs derivatives can derivatives not only retain the advantages of structure
alleviate the poor conductivity of PB/PBAs to a certain and composition of PB/PBAs, but also significantly
extent. Related works have attracted a lot of attention in enhance electrical conductivity, electrochemical activity,
recent years. Therefore, the design of PBAs components and stability after derivatization. In addition to the use of
| 287
hollow PB/PBAs as precursors, hollow structures are Therefore, PBAs are ideal precursors for the preparation
sometimes formed during the preparation of PB/PBAs of hollow polymetallic phosphides. In the existing litera-
derivatives. tures, the common methods for preparing TMPs based on
PBAs are generally solvent phosphating and gas phase
phosphating, and the latter is more common.
4.1 | Transition‐metal phosphide TMP is often used as HER catalyst. In addition, the
application of TMP in alkali solution for OER testing has
Transition‐metal phosphides (TMPs) have been widely attracted increasing attention in recent years. Zhang
used in narrow‐gap semiconductors[177] and electrocatalyst et al.[155] used NiCoFe PBA as the precursor and
materials. Because of their high catalytic performances and prepared polymetallic phosphide nanoparticles
low costs, TMPs are expected to replace the current noble (NiCoFe‐P‐NPs) and NiCoFe‐P‐NP@NiCoFe‐PBA nanoc-
metal catalysts. The performance of TMPs is mainly age composite by adjusting the heat treatment tempera-
determined by the interface chemistry and electronic ture and time of phosphide, respectively (Figure 11a–e).
structure. Based on the synergistic effect between various This composite material showed excellent electrocataly-
metals, the preparation of phosphides containing two or tic performance (Figure 11f). It can be seen from the
more metal elements can theoretically achieve more characterization results that the phosphating reaction
excellent catalytic performance. PBAs are not only easy to first occurs at the corner of the cube, and then continues
synthesize hollow structure, but also usually contain two or along the diagonal direction of the cube. PBA porous
more different kinds of metals in their composition. nanocages provide a stable structure for the composite as
F I G U R E 11 (a) Schematic illustration of synthetic processes of TMP@PBA composites and NiCoFe‐P nanocages from different
precursors. (b, c) SEM images of the NiCoFe‐P‐NP@NiCoFe‐PBA porous nanocages. (d, e) TEM image of the NiCoFe‐P‐NP@NiCoFe‐PBA
porous nanocages with a size about 360 nm. (f) LSV curves. (g) The stability testing of porous NiCoFe‐P‐NP@NiCoFe‐PBA nanocages before
and after 2000 cycles in 1.0 M KOH. Reproduced with permission: Copyright 2021, American Chemical Society.[155] (h) Schematic diagram
of the construction of hollow NiCoP. (i) GCD curves at 1 A g−1 of the NiCoP‐0‐500, NiCoP‐4‐400, NiCoP‐4‐500, NiCoP‐4‐600 and
NiCoP‐8‐500. (j) Cycle performance of the NiCoP‐4‐500 at 10 A g−1. Reproduced with permission: Copyright 2021, Elsevier.[118] PBA,
Prussian blue analog; SEM, scanning electron microscopy; TEM, transmission electron microscopy.
288 |
a structural support, and the porous nanocages of the recent years, people have paid more attention to
composite provide abundant metal active sites and good energy and environmental issues. TMOs has great
electronic structure. The synergistic effect between potential in energy storage and transformation, so it
cyanogen and TMPs makes the composite exhibit better has been widespread concerned. Porous TMOs can be
OER performance than traditional noble metal catalysts, prepared by using MOFs materials as precursors, and
with an overpotential of only 223 mV at a current density the porous structure has advantages of rich reaction
of 10 mA cm−2 and excellent stability in alkaline solu- interfaces and short diffusion paths. PBAs not only
tions (Figure 11g). In addition, NiFe‐P‐NP@NiFe‐PBA have the structural characteristics of MOFs materials,
and CoFe‐P‐NP@CoFe‐PBA composites were prepared but also usually contain a variety of metal compo-
and their OER performance was tested. The OER nents. Therefore, TMOs prepared using PBAs as
performance of bimetallic composites is far worse than templates also show some unique advantages, such
that of polymetallic composites, which can be attributed as uniform size, rich and variable morphology, easy
to the synergistic effect between different metal ions. He composition regulation, high porosity, large specific
et al.[156] also prepared Ni2P‐Co2P‐Fe2P hollow nanopr- surface area, etc.
ism (NiCoFeP‐HN). Different from the above synthesis Tian et al.[119] synthesized CuO/Co3O4 and Fe2O3
strategy, they first used in situ ion exchange method to materials with hollow/porous nanostructure using CuCo‐
construct hollow NiCoFeP‐PBA, and then phosphatized PBA and FeFe‐PBA as precursors (Figure 12a–f), respec-
it. The overpotential at 10 mA cm−2 current density is tively, and elucidated the formation mechanism of
294 mV, and the stability is good. In addition, the hollow CuO/Co3O4 in detail based on the Kirkendall
materials were used as the air electrode material of effect. During heat treatment, the external surface of
Zn‐air battery. The battery showed high energy density CuCo‐PBA precursor first adsorbs oxygen, and then
and better stability. reacts with it to form a CuO/Co3O4 shell. The diffusion
In addition to its outstanding performance as a rate of metal ions to the outside is larger than that of
catalyst for water splitting, TMP has also received a lot oxygen to the inside. Consequently, with increasing
of attention for its application in energy storage in recent reaction time, the void space will gradually form inside
years. Wang et al.[118] designed a NiCoP hollow nanobox PBA. The balance between electrons on the surface of
with a large specific capacity of 1590 F g−1 at 1 A g−1 PBA and adsorbed oxygen will generate an electric field
(Figure 11i) and exhibited excellent stability (Figure 11j). in the CuO/Co3O4 layer, which will attract more metal
Ni‐Co PBA nanoboxes were prepared by etching with ions to diffuse outward to the surface. When the reaction
ammonia, and then NiCoP‐x‐T was obtained by a series ends, CuO/Co3O4 composite with hollow/porous nanos-
of high temperature heat treatment with NaH2PO2·H2O tructure will be finally generated. In addition, the
(Figure 11h). First, the residual C after the heat asymmetric supercapacitor (ASC) is assembled by using
treatment process is evenly distributed on the surface CuO/Co3O4 and Fe2O3 as the cathode and anode,
of NiCoP, thus solving the problem of electrical respectively. The electrochemical test shows that the
conductivity. The DFT calculation results show that ASC not only has a high energy density of 48.77 W h
CoFeP has better conductivity than CoP and NiCo2O4. kg−1, but also exhibits excellent stability. Therefore, it
Second, the hollow structure helps to alleviate the has a certain practical application value. The excellent
volume change of electrode during the reversible electrochemical performance can be attributed to the
electrochemical reaction. Ma et al.[178] prepared a kind special hollow/porous nanostructure of the material,
of NiFeP nanoparticles assembled cubes by phosphating which has a larger active area and more active sites.
NiFe PBA at low temperature. As HER catalyst, the Furthermore, the ion transfer process can occur rapidly
overpotential at 10 mA cm−2 was only 82 mV. As super- with the help of pore channels. Ling et al.[120] synthe-
capacitor material, it shows high specific capacitance sized hollow MnO2 nanoboxes (H‐MnO2‐TEA) by using
(537.1 F g−1 at 1 A g−1) and excellent stability (91.3% of Mn‐PBA as a template through a simple triethanolamine‐
the initial capacitance after 5000 cycles of 1 A g−1). induced strategy. This synthesis strategy alleviates the
limiting problem of the electrochemical performance of
MnO2 due to its low surface area, slow kinetics, and poor
4.2 | Transition‐metal oxide stability, achieving a high specific capacitance of
316.8 F g−1 at 0.5 A g−1 as electrode material for super-
Transition‐metal oxides (TMOs) are inexpensive, capacitors. Zardkhoshoui et al.[121] obtained hollow
diverse and easy to prepare, which have a wide range MnFe2O4 by calcining MnFe‐PBA, and then CoS2
of applications in various fields, such as medicine, nanosheets are grown onto hollow MnFe2O4 by hydro-
sensing, energy storage and catalysis. Especially in thermal process (HMFO‐CSN). HMFO‐CSN shows a
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F I G U R E 12 (a) Schematic illustration of the synthetic process for hollow CuO/Co3O4 heterostructures derived from CuCo‐PBA and
transformation of CuCo‐PBA into CuO/Co3O4 based on the nanoscale Kirkendall effect. (b, c) SEM images of CuCo‐PBA nanocubes and
hollow CuO/Co3O4 nanoframes. (d–f) TEM images of hollow CuO/Co3O4 nanoframes, FeFe‐PBA nanoframes and Fe2O3 nanoframes.
Reproduced with permission: Copyright 2022, Royal Society of Chemistry.[119] (g) Schematic illustration of the fabrication process of
Ag@Co3O4 HNB. (h–j) TEM images of Co‐Co PBA quasi‐nanocubes, Co3O4 HNBs and Ag@Co3O4 HNBs. Reproduced with permission:
Copyright 2019, Elsevier.[90] PBA, Prussian blue analog; SEM, scanning electron microscopy; TEM, transmission electron microscopy.
capacity of 894 C g−1 at 1 A g−1 as electrode material for electrochemical performance than the traditional Li‐
supercapacitors. ion batteries anode materials.
Li‐ion battery is an efficient energy storage device, TMOs has been considered to have the potential to
and is also one of the most widely used energy storage replace noble metal catalysts, because TMOs has very
methods. The research on anode materials of Li‐ion strong catalytic activity and good stability for electro-
batteries has always attracted a lot of attention. catalytic reactions. Its controllable synthesis and rela-
Graphite is a widely used anode material, but its low tively simple preparation process are very suitable for
theoretical capacity and poor stability have prompted practical application. Wang et al.[151] designed Co3O4/Co‐
people to constantly look for new materials. The high Fe oxide double‐shelled nanoboxes with the MOF‐
theoretical capacity and low cost of TMOs make it hybrid‐assisted strategy. First, the ZIF‐67/Co‐Fe PBA
become a candidate anode material for Li‐ion batteries. core‐shell structure was successfully obtained by anion
However, in the process of charging and discharging, exchange method, and the Co3O4/Co‐Fe oxide double‐
the volume expansion caused by the insertion/extrac- shelled nanoboxes could be prepared by simple heat
tion of Li+ will results in the poor stability. To solve treatment in air. With the help of iron ion doping
these problems, researchers have designed a variety of through anion exchange process, the double‐layer
anode materials for Li‐ion batteries with hollow structure provides more active sites and stable structure,
structures, such as hollow tetrahedra, hollow hexahe- which makes the catalyst has higher catalytic activity and
dra and hollow microspheres. Guo et al.[90] heat‐treated stability. The synthesis strategy and experimental results
Co‐Co PBA to form Co3O4 hollow nanoboxes, and then also provide new ideas for the preparation of complex
deposited a layer of Ag nanoparticles uniformly on its hollow materials and their application in energy.
surface (Ag@Co3O4 HNB) (Figure 12g–i). This com-
posite has a high reversible theoretical capacity.
Moreover, the hollow structure solves the volume 4.3 | Transition‐metal sulfide
expansion problem, and Ag nanoparticles on the
surface improve the condctivity. The above advantages Transition‐metal sulfides (TMS) has been considered as a
make the Ag@Co3O4 composite show better potential catalyst for water splitting. In addition, in
290 |
recent years, a considerable number of studies have reaction at 120°C using Co‐Fe PBA as the precursor.
begun to focus on the prospect of TMS in energy storage Then, 2D MoS2 nanosheets were in situ grown on the
and conversion. In accordance with the modification surface of the nanoboxes at 200°C. The composite phase
strategy of transition metal phosphide materials, the was treated at 350°C for 2 h in N2 atmosphere to obtain
design of bimetallic or polymetallic sulfides with 3D Co3S4@MoS2 core‐shell heterostructure. To explore
homogeneous properties can theoretically obtain better the growth process of the material in the two‐step
electrochemical performance. The hollow structure will heating process, the author designed a series of experi-
bring larger specific surface area, thus increasing the ments. According to the experimental results, Co3S4
exposed active site, and will also increase the contact nanoboxe is synthesized by hydrothermal reaction at
area between the material and the electrolyte. TMS is 120°C for about 6 h, and no MoS2 nanosheet is generated
generally prepared by the calcination of sublimated in this process. When the temperature increased to
sulfur in a tube furnace for vulcanization, or by using 200°C, MoS2 began to grow on the surface of Co3S4
sulfur‐containing substances, such as Na2S or thioaceta- nanoboxes, and finally obtained Co3S4@MoS2 with core‐
mide (TAA), for vulcanization by hydrothermal/sol- shell heterostructure. Based on the synergistic effect
vothermal reactions.[179,180] These two methods are also between Co3S4@MoS2 heterostructure and 3D hollow
used when using PBAs as precursors to synthesize structure, a strong interfacial coupling between Co3S4
transition metal sulfides.[181] and MoS2 was established, which was beneficial to the
Yu et al.[122] successfully fabricated cubic NiS improvement of Co3S4@MoS2 catalytic performance. The
nanoframes using Ni‐Co PBA as template for anion OER overpotential was only 280 mV at 10 mA cm−2
exchange with S2− in Na2S at high temperature current density (Figure 13h). The HER overpotential was
(Figure 13a). The different reactivities of Ni‐Co PBA 136 mV at 10 mA cm−2 (Figure 13i).
edges and planes were used for anisotropic etching. The
process of anion exchange proceeds gradually with the
extension of reaction time (Figure 13b). It is proposed 4.4 | Transition‐metal selenide
that the ion exchange reaction first occurs at the edge of
the cube with high curvature and more defects. This is A series of transition‐metal selenide (TMSe), such as
because the rough edges have more defects and more MoSe2, FeSe2, NiSe2, CoSe2, etc., have gained wide
active sites, which is conducive to anion exchange attention due to their outstanding electrochemical
reactions. The NiS generated during the anion exchange performance. Nai et al.[148] designed a nanocage with
reaction will continuously deposit on the edge, forming a complex open structure using selective etching of
thin NiS shell, and the thickness of the shell will ammonia, and successfully prepared NiFe mixed selenide
continuously become thicker with the progress of the by heat treatment of nanocage with Se powder
reaction. The remaining smooth surface of the PBA, on (Figure 14a,b). The Ni–Fe mixed diselenide retains the
account of its rough exposed sides, is gradually com- cage‐like frame structure, and the surface is rougher.
pletely etched, resulting in the cubic NiS nanoframes This structure is wider, so that the active site can
with its unique morphology. Due to the high surface area contact the electrolyte more fully. The OER test results
and small particle structure, this NiS nanoframes exhibits show that the overpotential at 10 mA cm−2 is only
excellent electrochemical performance. After annealing, 240 mV (Figure 14c).
the 300 nm NiS nanoframes possesses a capacitance of Zhang et al.[87] prepared a hollow Co‐Co PBA
1290 F g−1 at 4 A g−1 (Figure 13c). In addition, the reaction nanoframe using a similar ammonia etching method as
conditions affecting the exchange of [Co(CN)6]3− and described above and selenized it. The resulting CoSe
S2− anions were studied. Na2S concentration, reaction (Figure 14d) was further treated by hydrothermal/
temperature and reaction time all affect the ion exchange solvothermal reactions for ion exchange. In the seleniza-
process and the formation of the nanoframes. tion reaction process, Se2− ions first react with Co2+,
Atomic doping and multicomponent integration are forming a thin layer of CoSe on the original hollow
effective strategies to obtain efficient bifunctional cata- nanoframe, which prevents the external Se2− from
lysts. The hybrid catalyst has high conductivity and more reacting with the internal Co2+. The Cu‐CoSe2
active exposed sites, so it will show enhanced catalytic (Figure 14e) obtained by doping CoSe2 with Cu exhibits
performance. Guo et al.[157] prepared a bifunctional slight lattice expansion, which may cause structural
catalyst Co3S4@MoS2 (Figure 13d–g) with high catalytic defects and high mobility, thus increasing the conductiv-
reactivity and excellent stability using a two‐step ity of the material. The open cage‐like hollow structure
temperature‐raising hydrothermal reaction process. helps alleviate the volume expansion problem caused by
First, hollow Co3S4 was prepared by hydrothermal Na+ during the insertion/extraction process. The capacity
| 291
F I G U R E 13 (a) Schematic illustration of the formation process of NiS nanoframes. (b) FESEM images of the products obtained after
reaction for 0 h, 0.5 h, 2 h and 6 h. Scale bars: 100 nm. 20 mg of Ni‐Co PB analogue nanocubes with size of 400 nm react with 40 mg of Na2S at
100°C for different durations. (c) Charge‐discharge curves at different current densities. Annealed NiS nanoframes with size of 300 nm are used
for capacitive measurements in 6 M KOH solution. Reproduced with permission: Copyright 2015, Wiley‐VCH.[122] (d) Schematic illustration for
the preparation of hollow Co3S4@MoS2 heterostructure via two‐step temperature‐raising hydrothermal procedure (I: Sulfidation, II: in situ MoS2
coating on the surface of Co3S4) and subsequent thermal annealing process under a N2 atmosphere (III). (e–g) SEM and TEM images of hollow
Co3S4@MoS2 heterostructure. (h) Polarization curves of Co3S4@MoS2, MoS2, Co3S4 and RuO2 electrodes for the OER in a 1 M KOH solution. (i)
Polarization curves of Co3S4@MoS2, MoS2, Co3S4 and Pt/C electrodes for the HER in a 1 M KOH solution. Reproduced with permission:
Copyright 2018, Elsevier.[157] PBA, Prussian blue analog; SEM, scanning electron microscopy; TEM, transmission electron microscopy.
can reach 470 mA h g−1 at a current density of 0.1 A g−1 anion doping modification methods have also attracted
(Figure 14f). Shirvani et al.[123] obtained bimetallic great attention. Song et al.[158] obtained Se‐doped cobalt
CoSe2/FeSe2 hollow nanocuboid nanostructures (CoSe2/ iron sulfide (Se‐(CoFe)S2) nanoboxes with hollow hetero-
FeSe2 HNCs) by selenizing CoFe‐PBA. CoSe2/FeSe2 structures/defects by sulfurizing and selenizing hollow
HNCs is a significant positive electrode material for high Co‐Fe PBA. Metal ions are positively charged and can
performance supercapacitors (332.75 mA h g−1 at capture OH− in the process of OER. The high electro-
1 A g−1). In addition to metal cation doping methods, negativity anion will reduce the electron density of the
292 |
F I G U R E 14 (a, b) FESEM and images of the Ni‐Fe mixed diselenide nanocages. (c) LSV curves of the six catalysts. Reproduced with
permission: Copyright 2017, WILEY‐VCH.[48] (d) SEM images of CoSe2 NFCs. (e) TEM images of Cu‐CoSe2 NFCs. (f) charge/discharge
profiles of Cu‐CoSe2 NFCs at 0.1 A g−1. Reproduced with permission: Copyright 2021, Elsevier.[49] SEM, scanning electron microscopy;
TEM, transmission electron microscopy.
metal in the metal compound. Therefore, doping the active sites in the reaction process, thus showing
high electronegativity anion will promote the balance of excellent chemical reactivity. In addition, the strong
chemisorption and dissociation reactions. In addition, ionic property of metal fluoride makes the metal cations
ion doping can modulate the intrinsic electronic struc- in it occupy a higher oxidation state.[182] Therefore, metal
ture and active site by overcoming the internal activation fluoride theoretically has a higher operating voltage and
energy during OER. Therefore, the heterogeneous a larger theoretical capacity, which makes it a potential
junction/defect Se‐(CoFe)S2 nanobox is a good catalyst electrode material for supercapacitors. As with other
material for OER and a potential supercapacitor material. kinds of metal compounds, the development of transition
This improvement method provides a new research idea metal fluorides is hindered by low electrical conductivity
for catalysis and energy storage materials. Although the and volume expansion during redox reactions. Based on
electrocatalytic performance of TMSe is good, there are the above problems, Zhang et al.[124] designed a NiF2/
certain risks in the selenization process. CoF2 composite with unique hollow cubic structure. The
electrochemical test results showed that the specific
capacitance of the material was 1491.1 F g−1 at 1 A g−1,
4.5 | Transition metal fluoride and the specific capacitance could still reach 1151.8 F g−1
at 10 A g−1 (Figure 15e). NiCo‐PBA was also used as the
Nonmetal anion and metal cations are usually connected precursor in the synthesis of this metal fluoride compos-
by covalent bonds, which is very unfavorable to the ite. Different from the common methods for preparing
formation of reactive active sites. Fluorine is the most PBAs derivatives, the precursor was not fluorinated
electronegative element in the periodic table. Therefore, directly. The intermediate NiCo‐NaOH was first obtained
in metal fluoride, the force between F and M is ionic with the help of hot alkaline solution. The reason is that
bond, which makes it easier for metal fluoride to form it is difficult to fluoridate NiCo‐PBA directly because
| 293
F I G U R E 15 (a, b) SEM images of NiCo‐PBA and NiCo‐NaOH. (c, d) SEM and TEM images NiF2/CoF2. (e) GCD curves at a current
density of 1 A g−1 of NiCo‐PBA, NiCo‐NaOH and NiF2/CoF2. Reproduced with permission: Copyright 2021, Elsevier.[81] (f, g) SEM
images of Fe‐Co‐PBA and Fe‐Co‐F‐400. (h, i) TEM images of Fe‐Co‐F‐400 and Fe‐Co‐F‐400 after stability test for OER. ( j, k) Polarization
curves of Fe‐Co‐PBA, IrO2 and Fe‐Co‐F samples loaded on a glassy carbon electrode (0.07 cm−2) in 1 M KOH solution at a scan rate of
5 mV s−1; and Tafel plots of Fe‐Co‐F samples and IrO2. (l) Stability test for Fe‐Co‐F‐400 by CV scanning before and after 1000 cycles (Inset:
Chronoamperometry measurement of Fe‐Co‐F‐400 at the potential of 1.48 V). Reproduced with permission: Copyright 2019, Elsevier.[91]
PBA, Prussian blue analog; SEM, scanning electron microscopy; TEM, transmission electron microscopy.
of the strong coordination effect between CN− and metal fluoride is usually porous material. The large
metal. Therefore, it is necessary to obtain Ni(OH)2 and surface area of porous materials can expose more active
[Co(CN)6]3− intermediates by ion exchange during hot sites, so transition metal fluorides are often used in
alkaline treatment, so as to facilitate subsequent fluori- electrocatalysis. Pei et al.[159] fluorinated Fe‐Co‐PBA at
dation. From the SEM results (Figure 15a,b), the surface 300°C, 400°C and 500°C, respectively, and further
of NiCo‐PBA treated with hot alkali becomes rough and explored the OER performance of the samples. The
slightly concave inward. Finally, the intermediate prod- results show that the fluoride obtained by heat treatment
uct is fluorinated with NH4F at 350°C in high purity Ar at 400°C has the best porous structure and morphology
atmosphere to obtain the target product (Figure 15c,d). (Figure 15f–i), the largest electrochemical active area,
The hollow structure not only increases the active site, and the best mass/ion diffusion transport channel. In
but also enables the ions and electrons to move rapidly, addition to the advantages of porous structure, the
so the electrochemical performance is improved. surface is rough and easily oxidized, which also enhances
Owing to the large number of defects and holes the OER activity and stability of the catalyst. The
etched in PBAs by NH4F during fluoridation, the final overpotential at 10 mA cm−2 was 250 mV, and the OER
294 |
F I G U R E 16 (a) Schematic illustration for the synthesis of NiCo@C microboxes. TEM images of (b) NiCo@C‐0, (c) NiCo@C−1, (d)
NiCo@C‐2 and (e) NiCo@C‐3. Reproduced with permission: Copyright 2020, Elsevier.[183] TEM, transmission electron microscopy.
performance was significantly improved compared with layer effectively protects the stability of the structure
that of the samples without fluoride treatment and prevents the aggregation of alloy particles. The
(Figure 15j,k). In addition, the LSV polarization curve structure of the sample with PR remained intact after
of the catalyst after 1000 cycles of CV test is basically calcination, and the agglomeration of the material was
unchanged compared with the original polarization relieved.
curve (Figure 15l), which is sufficient to show that the In summary, many works about hollow PBAs derivative
catalyst has not only high catalytic activity but also materials have been reported in recent years, because they
excellent stability. show remarkable excellent properties in the field of
electrochemistry. A variety of hollow structure PBAs
derivatives, such as TMPs, TMOs, TMS, etc. can be
4.6 | Alloy obtained through the derivative treatment of PBAs. It
should be noted that the process of PB/PBAs derivative
In addition to the above methods of introducing other treatment is not mild, because calcination or hydrothermal/
nonmetal into PBAs to prepare hollow metal deriva- solvothermal reactions are usually required. More impor-
tives, PBAs can be directly converted into derivatives tantly, derivative treatment often causes irreversible dam-
with high electrochemical activity by simple heat age to the material structure. Therefore, the improvement
treatment. Because of the abundance and low cost of of the stability of hollow structure in the process of
non‐noble metals, it is of great practical significance to derivative treatment should be further explored. In addi-
develop non‐noble metal catalysts to replace noble tion, the reasons for the structural changes and electro-
metal catalysts. Alloy materials contain two or more chemical performance improvement of PBAs derivatives
different kinds of metal elements, which have consider- should be clearly clarified with the help of advanced
able development prospects in the field of electrocata- characterization techniques and theoretical calculation
lysis because of the synergistic effect among the metals. methods.
Cui et al.[183] used the phenolic resin (PR) coated hollow
NiCo PBA microcubes etched by alkali. The NiCo PBA/
PR composite was further transformed into NiCo@C 5 | C O N C L U S I O N S AN D
microboxes under high temperature heat treatment OUTLOOK
(Figure 16a). TEM results (Figure 16b–e) revealed the
effect of PR on the structural stability of the materials. In this paper, several strategies for the preparation of
The structure of the samples without PR coating was hollow PB/PBAs are summarized, such as surfactant
seriously aggregated after heat treatment. The carbon regulation, chemical etching, and ion exchange. The
| 295
evolution process and the formation mechanism of hollow is more prone to collapse than solid structure, so it is
structure are analyzed and discussed. Hollow PB/PBAs and necessary to coordinate the relationship between electro-
related derived materials have been widely studied in the chemical performance and structural stability. 5) When
electrochemical field due to their own characteristics. For used as electrochemical energy storage materials, although
electrocatalyst materials, hollow structure has better the larger surface area is conducive to ion insertion/
catalytic performance than solid structure, because hollow extraction, it is easy to result in high irreversible capacity.
structure can expose more catalytic active sites. Moreover, High porosity is conducive to improve the rate performance
because of the synergistic effect between different metals in of materials. However, it will lead to the reduction of
bimetallic‐based or polymetallic‐based catalysts, the cata- volume specific capacity. Therefore, it is necessary to
lytic performance of bimetallic/polymetallic catalysts is control the porosity of hollow materials, and reduce the
usually better than that of monometallic catalysts. Hollow porosity as much as possible on the premise of ensuring
PBAs are ideal precursors for the preparation of bimetallic/ the smooth transmission of electrolytes. 6) At present, the
polymetallic catalysts because hollow PB/PBAs or related derivatization works are mainly about the complete
derivatives can be obtained by simple method and PBAs derivatization. After derivatization, PB/PBAs precursor
usually have two or more different transition metals. has undergone a complete transformation. For the
Hollow PBAs and related derivatives are also appropriate incomplete derivative products, some PB/PBAs can be
energy storage materials, because the 3D structure is retained while new components generate, which realize
conducive to ion insertion and extraction. Hollow structure the recombination of different components at nanometer
can increase the contact area between the material and scale. The synergistic effect of different components is
electrolyte, and alleviate the volume change during ion beneficial to the improvement of electrochemical perform-
insertion/extraction. The poor conductivity and poor ance. Such partially derived materials deserve further study.
stability of PBAs limit their applications. These problems
can be alleviated by the derivative treatment. Compared A U T H O R C O N TR I B U T I O N S
with PB/PBAs, the conductivity, electrochemical activity, Ying Wei: Conceptualization, data curation, writing‐
and stability of PB/PBAs derivatives are greatly improved. original draft, writing‐review & editing. Mingbo Zheng:
In conclusion, hollow PB/PBAs and hollow PB/PBAs Conceptualization, supervision, project administration,
derivatives have good application prospect in the electro- funding acquisition. Wei Zhu: Investigation. Huan
chemical field, and their performance can be further Pang: Project administration, funding acquisition.
improved by rational structure design and composition
regulation. AC KNOW LEDGM ENTS
Although numerous studies have explored the applica- This work was supported by the Natural Science Founda-
tions of hollow PB/PBAs and hollow PB/PBAs derivatives tion of Jiangsu Province (BK20200044), National Natural
in the field of electrochemistry in the last decade, several Science Foundation of China (U1904215), Open Fund of
problems should be further studied. 1) The types of PBAs National Joint Engineering Research Center for abrasion
studied so far are relatively limited, mainly focusing on control and molding of metal materials (HKDNM2019010),
several common transition metal elements, such as Mn, Fe, Program for Young Changjiang Scholars of the Ministry of
Co, and Ni. Therefore, expanding the types of metal Education, China (Q2018270), and the Fundamental
elements will bring more possibilities for structure regula- Research Funds for the Central Universities (NS2021039).
tion and performance improvement. 2) The morphology of We also acknowledged the Priority Academic Program
PB/PBAs is abundant, and changing the synthesis condi- Development of Jiangsu Higher Education Institutions and
tions will affect the morphology and size of the materials. the technical support we received at the Testing Center of
However, the specific reason of the structure changes and Yangzhou University.
the formation mechanism of hollow structures still need to
be further studied. In the future, some advanced character- C O NF L I C T O F I N T E R E S T S TA T E M E N T
ization methods can be used to explain the specific The authors declare no conflicts of interest.
mechanism. 3) Research works on hierarchical structures
are still relatively rare. It is desirable to design and regulate REFER ENCES
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| 299
[179] J. Zhao, Y. Zhang, X. Chen, G. Sun, X. Yang, Y. Zeng, research interests are in the field of materials for
R. Tian, F. Du, Adv. Funct. Mater. 2022, 32, 2206531.
electrochemical energy storage.
[180] J. Zhang, Y. Deng, Y. Wu, Z. Xiao, X. Liu, Z. Li, R. Bu,
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[181] R. Wang, C. Qian, Z. Zhang, H. Shen, J. Xia, D. Cui, K. Sun, Huan Pang received his PhD degree
H. Liu, C. Guo, F. Yu, J. Li, W. Bao, Small 2023, 19, 2206848. from Nanjing University in 2011. He is
[182] N. Devi, S. Ghosh, V. K. Perla, T. Pal, K. Mallick, New now a distinguished professor at
J. Chem. 2019, 43, 18369. Yangzhou University and a Young
[183] L. Cui, Y. Wang, X. Han, P. Xu, F. Wang, D. Liu, H. Zhao,
Changjiang Scholar of the Ministry of
Y. Du, Carbon 2021, 174, 673.
Education in China. He is a senior
member of the Chinese Chemical Society. He is the
AUTH OR BI OGRAPH IES
managing editor of EnergyChem, the editorial
board member of FlatChem and Rare Metals, and
Ying Wei is now a graduate student
the youth editorial board member of Nano
under Professor Zheng's supervision,
Research, Nano Research Energy, eScience,
Yangzhou University of chemistry
Advanced Fiber Materials among other distin-
and chemical engineering, China. Her
guished academic journals. He was recognized as
research mainly focuses on the field of
a highly cited researcher in Cross‐Field by Clarivate
the electrochemical energy storage
Analytics in 2020 and 2022. He has won “Best
materials and their applications.
Editor Award 2021” for his professional excellence
and outstanding contribution to Nano Research.
Mingbo Zheng received his PhD in
His research area mainly focuses on metal‐organic
material processing engineering from
frameworks (MOFs) related materials.
Nanjing University of Aeronautics and
Astronautics in 2009. He was a post-
doctoral researcher at Nanjing University
from 2009 to 2012. He was an associate
researcher at Nanjing University from 2012 to 2015. How to cite this article: Y. Wei, M. Zheng, W.
He worked at Yangzhou University from 2015 to Zhu, H. Pang, Carbon Neutralization
2020. He is currently an associate professor at Nanjing 2023;2:271–299. https://doi.org/10.1002/cnl2.64
University of Aeronautics and Astronautics. His

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Received: 31 January 2023 | Accepted: 5 April 2023

Hollow structures Prussian blue, its analogs, and

Ying Wei1 | Mingbo Zheng2 | Wei Zhu1 | Huan Pang1

Carbon Neutralization. 2023;2:271–299. onlinelibrary.wiley.com/r/carbon-neutralization | 271

1 | INTRODUCTION treatment cause mass loss. In this process, the internal

TABLE 1 Summary of PBA‐based electrode materials for rechargeable batteries.

2.2 | Supercapacitors combines the advantages of batteries and supercapaci-

TABLE 2 Summary of PBA‐based electrode materials for supercapacitors.

TABLE 3 Summary of PBA‐based electrode materials for OER/HER.

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