Hollow and substrate-supported Prussian blue, its analogs, and their derivatives for green water splitting

doi:10.1016/S1872-2067(21)63833-0

Abstract

Abstract:

To meet the current energy needs of society, the highly efficient and continuous production of clean energy is required. One of the key issues facing the green hydrogen evolution is the construction of efficient, low-cost electrocatalysts. Prussian blue (PB), Prussian blue analogs (PBAs), and their derivatives have tunable metal centers and have attracted significant interest as novel photo- and electrochemical catalysts. In this review, recent research progress into PB/PBA-based hollow structures, substrate-supported nanostructures, and their derivatives for green water splitting is discussed and summarized. First, several remarkable examples of nanostructured PB/PBAs supported on substrates (copper foil, carbon cloth, and nickel foam) and hollow structures (such as single-shelled hollow boxes, open hollow cages, and intricate hollow structures (multi-shell and yolk-shell)) are discussed in detail, including their synthesis and formation mechanisms. Subsequently, the applications of PB/PBA derivatives ((hydr)oxides, phosphides, chalcogenides, and carbides) for water splitting are discussed. Finally, the limitations in this research area and the most urgent challenges are summarized. We hope that this review will stimulate more researchers to develop technologies based on these intricate PB/PBA structures and their derivatives for highly efficient, green water splitting.

Key words: Prussian blue, Prussian blue analogues, Hollow structure, Substrate-supported structures, Green water splitting

Jing-Yi Xie, Bin Dong. Hollow and substrate-supported Prussian blue, its analogs, and their derivatives for green water splitting[J]. Chinese Journal of Catalysis, 2021, 42(11): 1843-1864.

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Figures/Tables 24

Fig. 1. (a) Three routes for industrial hydrogen production. Reproduced with permission from Ref. [19]. Copyright 2015, Royal Society of Chemistry; (b) Benchmarks for hydrogen- and oxygen-producing electrocatalysts for green water splitting. Reproduced with permission from Ref. [23]. Copyright 2015, American Chemical Society.

Fig. 2. Crystal structures of PB and PBAs. (a) A defect-free PB lattice. Reproduced with permission from Ref. [50]. Copyright 2012, Royal Society of Chemistry. Architectures of insoluble (b) and soluble (c) PB. Reproduced with permission from Ref. [47]. Copyright 2012, KISTI.

Table 1 Summary of the advantages and disadvantages of PB/PBAs.

Advantages	Disadvantages
Metal centers are tunable	Physical structures are unstable and prone to collapse at high temperatures
Secondary metallic species can be introduced to PB and PBA systems
Many derivatives possible, broadening the range of applications	PB and PBA particles cannot be scaled down to below 100 nm, preventing exposure of more active sites
Morphologies are tunable
Electron density is tunable

Fig. 3. (a) Schematic showing different strategies for the production of single-shelled boxes of PB/PBAs. I, soft templates; II, hard templates; III, chemical etching; and IV, cation exchange. (b,c) Transmission electron microscopy (TEM) micrographs of single-shelled PB at low and high magnification (synthesized via approach I). Reproduced with permission from Ref. [39]. Copyright 2009, American Chemical Society. (d,e) TEM images of a RbMnFe PBA obtained by approach II. Reproduced with permission from Ref. [95]. Copyright 2012, American Chemical Society. (f,g) Scanning electron microscopy (SEM) and TEM images of Co-Fe PBA single-shelled boxes after etching treatment (obtained by approach III). Reproduced with permission from Ref. [96]. Copyright 2012, Wiley-VCH. (h-j) TEM images showing the transformation of a solid Mn-Fe PBA cube to Co-Fe PBA single-shelled hollow boxes (obtained via approach IV). Reproduced with permission from Ref. [97]. Copyright 2017, Elsevier.

Fig. 4. (a) Schematic of the conversion of solid cubic PB precursor particles to Fe(OH)3/WO3-x·yH2O nanocages via etching. TEM (b) and SEM (c) images of Fe-W PBA. (d-f) SEM/energy dispersive X-ray (EDS) mapping of W, Fe, and O in Fe-W PBA cubes. Reproduced with permission from Ref. [106]. Copyright 2019, Royal Society of Chemistry.

Fig. 5. (a) Formation and subsequent morphological changes of NiS nanocages with holes in the centers of the faces. (b,c) Field-emission (FE)SEM images of NiS nanoframes. (d) TEM of a NiS particle. Reproduced with permission from Ref. [87]. Copyright 2015, Wiley-VCH. FESEM images (e) of single-crystalline KCoFe nanoframes; TEM image (f), selected area electron diffraction pattern (g), and high-resolution TEM images (h) showing the morphology and structure of a single KCoFe nanoframe. Reproduced with permission from Ref. [113]. Copyright 2017, AAAS. (i) Schematic of the formation of Ni-Co PBA nanocages with corner holes; FESEM (j) and TEM (k,l) images of Ni-Co PBA; FESEM (m) and TEM (n,o) images of Ni-Co oxide derivatives. Reproduced with permission from Ref. [114]. Copyright 2016, Wiley-VCH. (p) Schematic of the formation of Co-PBA cages; SEM (q) and TEM (r,s) images of Co-PBA cages; SEM (t) and TEM (u,v) images of cobaltosic oxide nanocages. Reproduced with permission from Ref. [88]. Copyright 2016, Royal Society of Chemistry.

Fig. 6. Nanocage with corner holes. (a) Schematic of the reaction process of hierarchical multi-shelled (approach A) and multicompositional (approach B) metal-oxide microboxes prepared from metal-organic framework templates. TEM images of Fe(OH)3 microboxes prepared from 0.02 (b) and 0.2 (c) M NaOH solution at room temperature; (d) TEM images of hierarchical Fe(OH)3 microboxes having a single shell prepared in 0.2 M NaOH solution in 80 °C; (e-g) TEM images of hierarchical Fe(OH)3 microboxes having multi-shells prepared in 2-4 M NaOH solution at 80 °C. Reproduced with permission from Ref. [91]. Copyright 2016, American Chemical Society. (h,i) SEM and TEM of yolk-shell PB. Reproduced with permission from Ref. [92]. Copyright 2019, Elsevier. (j,k) High-magnification SEM and TEM images of MnFe-PBA. Reproduced with permission from Ref. [90]. Copyright 2019, Elsevier.

Fig. 7. FESEM images of PBA-coated cobaltous hydroxide on NF after growth for 20 min (a), 1 h (b), 3 h (c), and 6 h (d); (e) Changes in the pH of solutions of 30 × 10-3 M K3Fe(CN)6 and cobaltous hydroxide during deposition on a NF electrode from 0 to 11 h. Reproduced with permission from Ref. [21]. Copyright 2019, Wiley-VCH. SEM images of Cu-FePBA/CF before (f) and after (g) acid etching; (h) TEM image of hollow acid-etched Cu-FePBA/CF; SEM images of PB/Fe (i), SnFePBA/Sn (j), ZnFePBA/Zn (k), NiFePBA/NF (l) samples, and APB/Fe (m), ASnFePBA/Sn (n), AZnFePBA/Zn (o), and ANiFePBA/NF (p) samples etched with acid. Reproduced with permission from Ref. [122]. Copyright 2019, Wiley-VCH.

Fig. 8. Summary of the advantages and disadvantages of the two PB/PBA design concepts.

Fig. 9. (a) SEM image of NiFeII-PBA obtained from NF calcined at 400 °C; (b) Linear sweep voltammetry curves in 1.0 M KOH containing NiFeII-PBA annealed from 300 to 800 °C. Reproduced with permission from Ref. [151]. Copyright 2018, American Chemical Society. (c) Schematic showing the thermal decomposition of small PB cubes, small hollow PB cubes, and large hollow PB cubes. Reproduced with permission from Ref. [152]. Copyright 2012, American Chemical Society. FESEM images of PBA cubes grown on different substrates. (d) Co3O4 nanosheets; (e) Ni(OH)2 nanoparticles; (f) NiCo2(OH)x nanosheets; (g) Co(OH)F nanowires; (h) MnO2 nanosheets; (i) Cu(OH)2 nanowires. Reproduced with permission from Ref. [21]. Copyright 2019, Wiley-VCH.

Fig. 10. (a) Schematic illustration of the shape-controlled synthesis of PBAs; (b) FESEM images of Mn1.0Fe0.8Co1.2O4; (c) Linear sweep voltammetry (LSV) curves obtained during the OER using MnxFe1.8-xCo1.2O4. Reproduced with permission from Ref. [155]. Copyright 2016, Royal Society of Chemistry; (d) Schematic of the low-temperature air plasma treatment of Co-PBA; (e) OER LSV of pristine and plasma-treated Co-PBA samples under industry-compatible conditions. Reproduced with permission from Ref. [156]. Copyright 2018, Wiley-VCH.

Fig. 11. (a) Schematic of the synthesis of FeP/HCNB. (b) TEM images of FeP/HCNB. Reproduced with permission from Ref. [159]. Copyright 2019, Elsevier. (c) Schematic of the synthesis of Fe-CoP nanocages. Reproduced with permission from Ref. [160]. Copyright 2020, Elsevier. (d) Schematic of the synthesis of porous Fe-CoP/NF; (e) Controlled-current electrolysis current density traces at different current densities for Fe-CoP/NF in alkaline media; (f) LSV curves of corresponding catalysts. Reproduced with permission from Ref. [161]. Copyright 2018, Wiley-VCH.

Fig. 12. (a) Schematic of the synthesis of Ni(OH)2, NiO, and Ni-P porous nanoplates from a NiNi-PBA; (b) TEM image of Ni-P porous nanoplates; (c) LSV curves of Ni-P, Ni(OH)2 and NiO porous nanoplates in alkaline media. Reproduced with permission from Ref. [166]. Copyright 2016, Royal Society of Chemistry. (d) Schematic of the synthesis of N-doped C/Ni5P4/Fe3P hollow cubes; (e) High-resolution TEM images of N-doped C/Ni5P4/Fe3P hollow cubes; (f) LSV plots of SiO2-coated N-doped C/Ni5P4/Fe3P hollow cubes and other samples for comparison. Reproduced with permission from Ref. [167]. Copyright 2017, Royal Society of Chemistry.

Fig. 13. SEM (a) and high-resolution TEM (b) images of hollow Co3S4@MoS2 heterostructures; (c) Polarization curves of Co3S4@MoS2, MoS2, Co3S4, and RuO2 electrodes for the OER in 1.0 M KOH; (d) Polarization curves of Co3S4@MoS2, MoS2, Co3S4, and Pt/C electrodes for the HER in a 1 M KOH solution. Reproduced with permission from Ref. [181]. Copyright 2018, Elsevier. (e) Schematic display of the synthesis of (Ni,Co)Se-GA for water splitting electrocatalysis. (Ni,Co)Se2-GA decorated on Ni foam for OER (f) and HER (g) electrocatalysis in 1.0 M KOH solution, as well as (Ni,Co)Se2, GA, and RuO2 for comparison. Reproduced with permission from Ref. [183]. Copyright 2017, American Chemical Society. (h) Fabrication steps for Co9S8@NC hybrid composites; (i) LSV plots of Co9S8. Reproduced with permission from Ref. [170]. Copyright 2018, Royal Society of Chemistry.

Fig. 14. (a) Schematic of the construction of Ti-Fe mixed sulfide nanoboxes; (b) TEM images of the Ti-Fe PBA nanoboxes; LSV curves (c), and chronopotentiometry (d) of the c-Ti-Fe-S nanobox catalyst. Reproduced with permission from Ref. [184]. Copyright 2018, Royal Society of Chemistry.

Fig. 15. (a) Schematic of the fabrication of carbon-coated hollow mesoporous FeP microcubes; (b) high-resolution TEM image of carbon-coated hollow mesoporous FeP@C microcube; (c) Polarization curves of Pt/C, carbon-coated hollow mesoporous FeP microcubes, FeP nanoparticles, and carbon-coated hollow Fe3O4 microcubes in acidic media. Reproduced with permission from Ref. [191]. Copyright 2016, Royal Society of Chemistry. (d) Schematic of the preparation of Co@Co-N/rGO. (e) LSV curves for different catalysts in 1 M KOH solution. Reproduced with permission from Ref. [192]. Copyright 2019, Elsevier. (f) Schematic of the preparation of O-CNT/NiFe. Reproduced with permission from Ref. [193]. Copyright 2020, American Chemical Society.

Fig. 16. (a,b) Schematic of the preparation of hollow and bamboo-like structures at various annealing temperatures. (c) LSV plots of the encapsulated nanostructures in 0.1 M KOH. Reproduced with permission from Ref. [194]. Copyright 2016, Royal Society of Chemistry. (d,e) Schematic display of the ultrafast microwave-assisted preparation of M@NC/rGO, as well as a corresponding TEM image; (f) IR-Corrected polarization curves of FeNi@NC/RGO, FeNi/HRGO, FeNi@NC, and IrO2. Reproduced with permission from Ref. [195]. Copyright 2018, Royal Society of Chemistry.

Fig. 17. Schematic of HER (left) and OER (right) polarization curves for water electrolysis. The cathode (ηc) and anode (ηa) potentials require the same current density (j).

Fig. 18. Schematic of the HER and OER in acidic and alkaline solutions.

Fig. 19. (a) Schematic demonstration of the formation of Co-PBA/CdS (beaded structure); (b) EDS elemental mapping of Co, N, Cd, and S in Co-PBA/CdS synthesized at relatively low temperatures with 82.6 wt% Co-PBA (PB-Co/CdS-LT-3); (c,d) Photocatalytic hydrogen evolution rates and catalytic durability of PB-Co/CdS-LT-3. Reproduced with permission from Ref. [254]. Copyright 2021, American Chemical Society.

Fig. 20. (a) Schematic demonstration of two-step sulfidation for the synthesis of CdS frame-in-cage particles; TEM images of Cd-PBA cubes (b), Cd-PBA cube-in-CdS cage particles (c), and CdS frame-in-cage particles (d); (e) PHE rates of CdS cubes, CdS cages, and CdS frame-in-cage particles. Reproduced with permission from Ref. [258]. Copyright 2020, Wiley-VCH.

Table 2 Summary of the PHE performances of representative PBA-derived photocatalysts.

Catalyst	Sacrificial reagent	PHE rate (μmol h^-1 g^-1)	Ref.
PB-Co/CdS-LT-3	Lactic acid	57228	[254]
CdS frame-in-cage particles	Na₂S and Na₂SO₃	13600	[258]
g-C₃N₄-7% Fe₂N	TEOA	88.7	[263]
CdS-YS	Na₂S and Na₂SO₃	3051.4	[264]
FNS@ZIS-2	—	10465	[265]
Cd_0.5Zn_0.5S	Na₂SO₃ and Na₂S	4341.6	[266]
PBA-TiO₂ (Janus)	TEOA and NaIO₃	198	[267]

Table 3 Summary of the HER activities of several PB/PBAs-based electrocatalysts in different electrolytes.

Electrocatalyst	j (mA cm^-2)	η (mV)	Tafel slope (mV dec^-1)	Electrolyte	Ref.
Co₃S₄@MoS₂	10	136	74	1 M KOH	[181]
(Ni,Co)Se₂-GA	10	128	70	1 M KOH	[183]
P-Co_0.9Ni_0.9Fe_1.2 NCs	10	200.7	50.5	1 M KOH	[162]
nPBA@Co(OH)₂/NF	10	290	130	1 M KOH	[21]
Fe-Co_xP NCs	10	127	55	0.5 M H₂SO₄	[57]
P-S-24	10	61	67	1 M KOH	[286]
MoS₂-NiNi PBA	10	144	39.5	0.5 M H₂SO₄	[65]
CNBO-NSs	10	140	116	1 M KOH	[66]
NCF-MOF	10	270	114	0.1 M KOH	[67]
FeP/GA	10	150	65	0.5 M H₂SO₄	[71]
	10	240	142	1 M KOH
MoS₂-NiNi PBA	10	144	39.5	0.5 M H₂SO₄	[65]
Co@NG-acid	10	200	112	1 M KOH	[287]
FeCo	10	149	77	1 M KOH	[288]
NCF-MOF	10	270	114	0.1 M KOH	[289]
Ni-Co-P-300	10	150	60.6	1 M KOH	[290]
Fe-CoP HTPAs	10	98	90	1 M KOH	[291]
MoP@PC	10	51	45	0.5 M H₂SO₄	[292]
FeP/GA	10	150	65	1 M KOH	[293]
(Ni,Co)Se₂-GA	10	128	79	1 M KOH	[294]
Fe-Co_xP NCs	10	125	55	0.5 M H₂SO₄	[57]
Ni-Co-MoS₂	10	155	51	0.5 M H₂SO₄	[295]
Ni-Fe-P	10	98	50	1 M KOH	[296]
Ni₂P/NiCoP@NCCs	10	116	79	1 M KOH	[297]
Co_0.6Fe_0.4P	10	133	61	1 M KOH	[298]
Co@Co-N/rGO	10	180	43	1 M KOH	[192]
FeP NPs	10	115	56	1 M KOH	[299]
Mn_0.6Co_0.4P-rGO	10	54	63	1 M KOH	[300]
Fe-CoP	10	78	92	1 M KOH	[161]

Table 4 Summary of the OER activities of PB/PBAs-based electrocatalysts in different electrolytes.

Electrocatalyst	j (mA cm^-2)	η (mV)	Tafel slope (mV dec^-1)	Electrolyte	Ref.
Co₃S₄@MoS₂	10	280	43	1 M KOH	[181]
(Ni,Co)Se₂-GA	10	250	70	1 M KOH	[183]
Co₉S₈@NC-800	10	≈302	67	0.1 M KOH	[170]
Fe-CoP/NF	10	190	36	1 M KOH	[161]
P-Co_0.9Ni_0.9Fe_1.2 NCs P-S-NiFe NCs P-NiFe-800 NPs CoP/NC	10 10 10 10	273.1 270 270.1 350	46.9 35 39 57	1 M KOH 1 M KOH 1 M KOH 1 M KOH	[162] [163] [164] [165]
Fe-CoP cage Ni-Co PBA cages NiFe/NF nPBA@Co(OH)₂/NF CuFe oxide/CF (Ni,Co)Se₂ (NiFe)PS₃ P-S-24 FCN-40-P NiFe(OH)_x/CP	10 10 80 20 20 10 10 10 100 10 10	300 380 270 270 270 300 278 275 268 265 261	35.2 50 28 33 46 68 65 41.7 27 52 33.8	1 M KOH 1 M KOH 1 M KOH 0.1 M KOH 1 M KOH 1 M KOH 1 M KOH 1 M KOH 1 M KOH 1 M KOH 1 M KOH	[160] [114] [120] [21] [122] [56] [58] [286] [59] [60]
FeCoP-400 NixCo₃-xO₄/NF Fe-Co-F-400 Fe-NiO/CC CNBO-NSs NCF-MOF CoSe₂ NBs O-NiFe@C-600	100 10 10 10 10 10 10 10 10	303 261 287 250 218 300 320 335 300	33.8 50 88 38.3 47 60 119 54.2 56.72	1 M KOH 1 M KOH 1 M KOH 1 M KOH 1 M KOH 1 M KOH 0.1 M KOH 1 M KOH 1 M KOH	[61] [62] [63] [64] [66] [67] [68] [69]
CoFe@NC-NCNT-H	10	380	99.6	0.1 M KOH	[70]

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