Perfecting HER catalysts via defects: Recent advances and perspectives

doi:10.1016/S1872-2067(24)60105-1

Abstract

Abstract:

Defect engineering has become a promising approach to improve the performance of hydrogen evolution reaction (HER) catalysts. Non-noble transition metal-based catalysts (TMCs) have shown significant promise as effective alternatives to traditional platinum-group catalysts, attracting considerable attention. However, the industrial application of TMCs in electrocatalytic hydrogen production necessitates further optimization to boost both catalytic activity and stability. This review comprehensively examines the types, fabrication methods, and characterization techniques of various defects that enhance catalytic HER activity. Key advancements include optimizing defect concentration and distribution, coupling heteroatoms with vacancies, and leveraging the synergy between bond lengths and defects. In-depth discussions highlight the electronic structure and catalytic mechanisms elucidated through in-situ characterization and density functional theory calculations. Additionally, future directions are identified, exploring novel defect types, emphasizing precision synthesis methods, industrial-scale preparation techniques, and strategies to enhance structural stability and understanding the in-depth catalytic mechanism. This review aims to inspire further research and development in defect-engineered HER catalysts, providing pathways for high efficiency and cost-effectiveness in hydrogen production.

Key words: Defect, Hydrogen evolution reaction, Catalytic mechanism, Synergistic catalysis, Transition metal-based catalyst

Chengguang Lang, Yantong Xu, Xiangdong Yao. Perfecting HER catalysts via defects: Recent advances and perspectives[J]. Chinese Journal of Catalysis, 2024, 64: 4-31.

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Figures/Tables 22

Scheme 1. The schematic illustration of employing defects and modulations for electrocatalytic HER.

Fig. 1. (a) Schematic illustration of the synthesis of defective NiSe2. (b) The electron paramagnetic resonance spectra of NiSe2-VSe/CC and NiSe2/CC. Reproduced with permission from Ref. [50]. Copyright 2023, American Chemical Society. (c) EPR spectra of NiCoP, A-NiCoP and A-NiCoP|S-20. (d) XPS spectra of S 2p in A-NiCoP|S-20. Reproduced with permission from Ref. [51]. Copyright 2020, Elsevier. (e) SEM characterization of CVD grown MoS2 with oxygen plasma treatment. Reproduced with permission from Ref. [52]. Copyright 2016, American Chemical Society. (f) Schematic illustration for the experimental setup of inductively coupled plasma. (g) XPS spectra of Mo 3d and S 2p before and after H2 plasma treatment. Reproduced with permission from Ref. [53]. Copyright 2016, John Wiley and Sons.

Fig. 2. (a) Schematic representation of the fabrication process for monolayer MoS? nanomesh featuring defective atomic-sized pores in the basal plane. HRTEM image (b) and corresponding FFT image (c) of defective MoS2 nanomesh. Reproduced with permission from Ref. [66]. Copyright 2018, Elsevier. (d) Schematic illustration for fabricating NiTiO3/TM via ball milling. (e) Raman spectra of in situ NiTiO3/Ni, ex situ NiTiO3/Ni, ball-milled NiTiO3, and pristine NiTiO3. (f) XPS spectra of Ti 2p and O 1s from in situ NiTiO3/Ni and NiTiO3. Reproduced with permission from Ref. [67]. Copyright 2020, Royal Society of Chemistry.

Fig. 3. (a) Ni K-edge XANES for Ni3S2 and Ni3S2-VNi. (b) The differential charge density of Ni3S2-VNi (blue and yellow areas represent the electron-poor regions and the electron-rich regions, respectively). Reproduced with permission from Ref. [69]. Copyright 2022, Elsevier. (c) HAADF-STEM image of NiCoP-MoS2-VMo. (d) Electronic intensity profiles of the numbered line marked in (c). (e) EPR spectra of MoS2, Ni-MoS2, and NiCoP-MoS2-VMo. Reproduced with permission from Ref. [75]. Copyright 2022, American Chemical Society. (f) The synthesis of inverse opal-like Mo2C via the hard template method employing SiO2. Reproduced with permission from Ref. [73]. Copyright 2017, American Chemical Society.

Fig. 4. (a) Schematic diagram of the synthesis process of Vo-Co3O4@NF and Vs-Co3S4@NF. (b) EPR spectra of Co3O4@NF, Vo-Co3O4@NF, Co3S4@NF, and Vs-Co3S4@NF. Reproduced with permission from Ref. [80]. Copyright 2023, Elsevier. (c) ADF-STEM images of coalesced Se mono-vacancies induced by increasing the H2 concentration. Reproduced with permission from Ref. [85]. Copyright 2023, Elsevier. (d) High-resolution Ti 2p3/2 XPS spectra of TiO2 and TiO1.23. Reproduced with permission from Ref. [87]. Copyright 2016, American Chemical Society.

Fig. 5. (a) Schematic illustration of the synthetic process of TiVCO. (b) HAADF-STEM image of TiVCO with Ti vacancies marked by red circles. (c) Corresponding intensity profiles of Ti along the yellow line in (b). Reproduced with permission from Ref. [92]. Copyright 2023, John Wiley and Sons. (d) The synthetic illustration of the single Pt anchored defective CoSe2 via photoreduction method. (e) The unprocessed HAADF-STEM image of CoSe2-x-Pt. (f) The processed and colored HAADF-STEM image of CoSe2-x-Pt. (g) 2D atomic arrangement of bright Co atoms on (210) plane and of dark Co and Se atoms underneath (210) plane. Reproduced with permission from Ref. [42]. Copyright 2018, John Wiley and Sons.

Fig. 6. (a,b) The STEM image and the line profiles extracted from the areas marked by purple rectangles of the monolayer MoS? after etching. (c) EPR spectra of etched MoS2 with different etching durations compared to P-MoS2. Reproduced with permission from Ref. [94]. Copyright 2020, American Chemical Society. (d) Schematic representation for the preparation of Mo vacancy-rich MoP electrocatalyst. (e) EPR spectra. Reproduced with permission from Ref. [95]. Copyright 2023, Elsevier. (f,g) High-resolution XPS spectra of Ni 2p and P 2p. (h) Niδ+ and Pδ- percentages in nickel phosphides. Reproduced with permission from Ref. [98]. Copyright 2020, John Wiley and Sons.

Fig. 7. (a) Ni K-edge XAFS curves. (b) Fourier transformed k2-weighted EXAFS spectra. Reproduced with permission from Ref. [105]. Copyright 2018, American Chemical Society. Pt L3-edge (c) and radial distance χ(R) space spectra (d) with Pt foil and PtO2 as references. Wavelet transforms (WT) of Pt foil (e), and Pt of Pt-Ni2Fe1-24 (f). Reproduced with permission from Ref. [106]. Copyright 2022, John Wiley and Sons.

Fig. 8. (a) In situ Raman spectra of NiFe LDH during HER process in 1 mol L-1 KOH. (b) Magnified view of the corresponding orange wavelength region in (a). (c) Schematic illustration for the reaction mechanism of HER on NiFe LDH. Reproduced with permission from Ref. [108]. Copyright 2019, Royal Society of Chemistry. (d) In situ XANES spectra at Mo K-edge. (e) XANES spectra at Ni K-edge. (f) First-derivative spectra, and (g) Fourier-transformed R-space spectra (open points) and fits (solid lines) of Ni@1T-MoS2. Reproduced with permission from Ref. [110]. Copyright 2020, Springer Nature.

Fig. 9. Mechanisms of HER electrocatalysis in acidic and alkaline media.

Table 1 Reaction steps for HER in acidic and alkaline media.

Catalytic reaction step	Acidic solution	Alkaline solution	Surface reaction step
Volmer step	H⁺+ e^-+ ^→ H^	H₂O + e^- + ^* → H^* + OH^-	adsorption step
Heyrovsky step	H^+ H⁺+ e^-→ H₂+ ^	H₂O + e^- + H^* → H₂ + OH^- + ^*	desorption step
Tafel step	2H^* → H₂ + 2^*	2H^* → H₂ + 2^*	desorption step
Overall reaction	2H⁺+2e^-→ H₂	2H₂O + 2e^- → H₂ + OH^-

Table 2 Summary of catalysts modified by defect strategies.

Catalyst	Method	Defect type	Characterization technique	Electrolyte	Overpotential at 10 mA cm^-1	Ref.
NiMoO₄	N₂ plasma	S vacancies, Pt doping	XAS, EPR, XPS	1 mol L^-1 KOH	71 mV	[188]
Vs-CoS₂/CC	Ar Plasma	S vacancies	EPR, XPS, HRTEM	1 mol L^-1 KOH	170 mV	[189]
MoS₂	O₂ Plasma	O doping	XPS, Raman	0.5  mol L^-1 H₂SO₄	131 mV	[190]
N,Pt-MoS₂	N₂ plasma	N,Pt doping	HADDF-STEM, XPS, EPR, XAS	1 mol L^-1 KOH	38 mV	[191]
Bi₂O₃	plasma irradiation	O vacancies	EPR, XPS, Raman	1 mol L^-1 KOH	174 mV	[192]
MoS₂	Ar plasma	S vacancies	Raman, ACTEM	0.5 mol L^-1 H₂SO₄	170 mV	[193]
Pt/TiO_2-_X	plasma sputtering	atomic Pt doping	XPS, XAS, HAADF-STEM	0.5 mol L^-1 H₂SO₄	95 mV	[166]
NiSe₂-V_Se	Ar plasma	Se vacancies	XPS, EPR	1 mol L^-1 KOH	91 mV	[50]
NiCoP	Ar plasma	S doping, P vacancies	EPR, XPS	1 mol L^-1 KOH	88 mV	[51]
Ni₃S₂-V_Ni	sacrificial dopants	Ni vacancies	EPR, XPS, XAS	1 mol L^-1 KOH	35 mV	[69]
NiCoP-MoS₂-V_Mo	sacrificial dopants	Mo vacancies	HAADF-STEM, EPR, XPS, XAS	1 mol L^-1 KOH	67 mV	[75]
FeP	sacrificial dopants	Fe vacancies	XPS	0.5 mol L^-1 H₂SO₄	65 mV	[68]
CoNiP-V	sacrificial dopants	Co/Ni vacancies	XPS, EPR	1 mol L^-1 KOH	58 mV	[194]
MoxC-IOL	sacrificial dopants	Mo vacancies	XPS,	1 mol L^-1 KOH	82 mV	[73]
MoS₂ nanomesh	ball milling	S vacancies	XPS, EPR	0.5 mol L^-1 H₂SO₄	160 mV	[66]
NiTiO₃/Ni hybrid	ball milling	O vacancies	XPS, EPR	1 mol L^-1 KOH	10 mV	[67]
Ru@D-MoS₂	ball milling	Ru doping, S vacancies	HAADF-STEM, XPS, XAS	1 mol L^-1 KOH	107 mV	[62]
NiPS₃	ball milling	Ni,S dual vacancies	XPS, XAS	1 mol L^-1 KOH	124 mV	[195]
MoC/Mo₂C	ball milling	N doping	XPS	1 mol L^-1 KOH	112 mV	[196]
SrTi_0.7Ru_0.3O_3‒_δ	ball milling	O vacancies	XAS, XPS, EPR	1 mol L^-1 KOH	46 mV	[197]
WTe₂	electrochemical method	Te vacancies	XPS and UPS	0.5 mol L^-1 H₂SO₄	119 mV	[143]
MoS₂	electrochemical method	S vacancies	XPS	1 mol L^-1 KOH	n/a	[90]
TiO_1.23	electrochemical method	O vacancies	XPS	0.5 mol L^-1 H₂SO₄	198 mV	[87]
LaCoO₃	electrochemical method	O vacancies	XAS, XPS	1 mol L^-1 KOH	238 mV	[198]
Cu-FeOOH/Fe₃O₄	electrochemical method	O vacancies	XAS, XPS, EPR	1 mol L^-1 KOH	n/a	[199]
N-Vo-NiMoO₄	chemical method	N doping, O vacancies	XPS, EPR	1 mol L^-1 KOH	55 mV	[200]
MoS₂	chemical method	S vacancies	STEM, EPR, XPS, XAS	0.5 mol L^-1 H₂SO₄	131 mV	[94]
C-MoS₂	chemical method	C doping	XPS, XAS	1 mol L^-1 KOH	45 mV	[201]
CoS₂	chemical method	S vacancies, P doping	XAS, EPR, XPS	0.5 mol L^-1 H₂SO₄	57 mV	[202]
MoSe₂	chemical method	Mn doping, Se vacancies	HAADF-STEM	0.5 mol L^-1 H₂SO₄	167 mV	[203]
Mo-doped V_1.11S₂	chemical method	Mo doping, V vacancies	Raman, XPS, EPR	0.5 mol L^-1 H₂SO₄	160 mV	[77]

Table 2 Summary of catalysts modified by defect strategies.

Catalyst	Method	Defect type	Characterization technique	Electrolyte	Overpotential at 10 mA cm^-1	Ref.
NiMoO₄	N₂ plasma	S vacancies, Pt doping	XAS, EPR, XPS	1 mol L^-1 KOH	71 mV	[188]
Vs-CoS₂/CC	Ar Plasma	S vacancies	EPR, XPS, HRTEM	1 mol L^-1 KOH	170 mV	[189]
MoS₂	O₂ Plasma	O doping	XPS, Raman	0.5  mol L^-1 H₂SO₄	131 mV	[190]
N,Pt-MoS₂	N₂ plasma	N,Pt doping	HADDF-STEM, XPS, EPR, XAS	1 mol L^-1 KOH	38 mV	[191]
Bi₂O₃	plasma irradiation	O vacancies	EPR, XPS, Raman	1 mol L^-1 KOH	174 mV	[192]
MoS₂	Ar plasma	S vacancies	Raman, ACTEM	0.5 mol L^-1 H₂SO₄	170 mV	[193]
Pt/TiO_2-_X	plasma sputtering	atomic Pt doping	XPS, XAS, HAADF-STEM	0.5 mol L^-1 H₂SO₄	95 mV	[166]
NiSe₂-V_Se	Ar plasma	Se vacancies	XPS, EPR	1 mol L^-1 KOH	91 mV	[50]
NiCoP	Ar plasma	S doping, P vacancies	EPR, XPS	1 mol L^-1 KOH	88 mV	[51]
Ni₃S₂-V_Ni	sacrificial dopants	Ni vacancies	EPR, XPS, XAS	1 mol L^-1 KOH	35 mV	[69]
NiCoP-MoS₂-V_Mo	sacrificial dopants	Mo vacancies	HAADF-STEM, EPR, XPS, XAS	1 mol L^-1 KOH	67 mV	[75]
FeP	sacrificial dopants	Fe vacancies	XPS	0.5 mol L^-1 H₂SO₄	65 mV	[68]
CoNiP-V	sacrificial dopants	Co/Ni vacancies	XPS, EPR	1 mol L^-1 KOH	58 mV	[194]
MoxC-IOL	sacrificial dopants	Mo vacancies	XPS,	1 mol L^-1 KOH	82 mV	[73]
MoS₂ nanomesh	ball milling	S vacancies	XPS, EPR	0.5 mol L^-1 H₂SO₄	160 mV	[66]
NiTiO₃/Ni hybrid	ball milling	O vacancies	XPS, EPR	1 mol L^-1 KOH	10 mV	[67]
Ru@D-MoS₂	ball milling	Ru doping, S vacancies	HAADF-STEM, XPS, XAS	1 mol L^-1 KOH	107 mV	[62]
NiPS₃	ball milling	Ni,S dual vacancies	XPS, XAS	1 mol L^-1 KOH	124 mV	[195]
MoC/Mo₂C	ball milling	N doping	XPS	1 mol L^-1 KOH	112 mV	[196]
SrTi_0.7Ru_0.3O_3‒_δ	ball milling	O vacancies	XAS, XPS, EPR	1 mol L^-1 KOH	46 mV	[197]
WTe₂	electrochemical method	Te vacancies	XPS and UPS	0.5 mol L^-1 H₂SO₄	119 mV	[143]
MoS₂	electrochemical method	S vacancies	XPS	1 mol L^-1 KOH	n/a	[90]
TiO_1.23	electrochemical method	O vacancies	XPS	0.5 mol L^-1 H₂SO₄	198 mV	[87]
LaCoO₃	electrochemical method	O vacancies	XAS, XPS	1 mol L^-1 KOH	238 mV	[198]
Cu-FeOOH/Fe₃O₄	electrochemical method	O vacancies	XAS, XPS, EPR	1 mol L^-1 KOH	n/a	[199]
N-Vo-NiMoO₄	chemical method	N doping, O vacancies	XPS, EPR	1 mol L^-1 KOH	55 mV	[200]
MoS₂	chemical method	S vacancies	STEM, EPR, XPS, XAS	0.5 mol L^-1 H₂SO₄	131 mV	[94]
C-MoS₂	chemical method	C doping	XPS, XAS	1 mol L^-1 KOH	45 mV	[201]
CoS₂	chemical method	S vacancies, P doping	XAS, EPR, XPS	0.5 mol L^-1 H₂SO₄	57 mV	[202]
MoSe₂	chemical method	Mn doping, Se vacancies	HAADF-STEM	0.5 mol L^-1 H₂SO₄	167 mV	[203]
Mo-doped V_1.11S₂	chemical method	Mo doping, V vacancies	Raman, XPS, EPR	0.5 mol L^-1 H₂SO₄	160 mV	[77]

Fig. 10. (a) The HAADF-STEM images of the WO3 and WO2.9. (b) The free energy diagram of HER for variously active sites on WO3(001) and WO2.9(010). Reproduced with permission from Ref. [141]. Copyright 2015, Springer Nature. (c) In situ ATR-FTIRS of *H bands recorded on S sites in NiS2. Reproduced with permission from Ref. [142]. Copyright 2024, Springer Nature. (d) Schematic description of HER process in AV- and CV-MoSe2. (e) Schematic illustration of Volmer-Tafel reaction pathway of HER. Reproduced with permission from Ref. [85]. Copyright 2019, Elsevier. Comparison of (f) Projected density of state of the Ni d orbit. (g) LSV curves of NiSe2/CC, NiSe2-VSe/CC, and Pt/C. Reproduced with permission from Ref. [50]. Copyright 2023, American Chemical Society.

Fig. 11. (a) The EPR spectra of Ni3S2 and Ni3S2-VNi/NF using Zn as sacrificial dopant. (b) Ni K-edge XANES of Ni3S2-VNi and Ni3S2. Reproduced with permission from Ref. [69]. Copyright 2022, Elsevier. (c) DOS calculated for δ-FeOOH NSs with and without VFe. (d) Schematic illustration of hydrogen evolution on the Fe2 site of the δ-FeOOH surface with VFe. (e) LSV curves of fabricated catalysts in 1.0 mol L?1 KOH solution. Reproduced with permission from Ref. [145]. Copyright 2018, John Wiley and Sons.

Fig. 12. (a) High-resolution transmission microscope images of four types of vacancies in the samples: VMo, VSe, VSe2, and VMoSe2. Reproduced with permission from Ref. [147]. Copyright 2018, American Chemical Society. (b) Pair distribution function analysis of pristine NiFe LDH and v-NiFe LDH. (c) Ni K-edge and (d) Fe K-edge Fourier transforms (FT) results for NiFe LDH and v-NiFe LDH. (e) HER performance of v-NiFe LDH at neutral pH. Reproduced with permission from Ref. [148]. Copyright 2019, American Chemical Society.

Fig. 13. HAADF-STEM images (a) and the k2-weighted EXAFS spectra (b) of atomic Pt uniformly disperse in the 2D MoS2. Reproduced with permission from Ref. [161]. Copyright 2015, Royal Society of Chemistry. (c) HR-TEM images of the layered structure of Pt/TiO2-X catalyst. (d) Electrochemical HER activity and stability of Pt/TiO2-X electrocatalyst. Reproduced with permission from Ref. [166]. Copyright 2021, Elsevier. (e,f) The influence of the Bader charge (ΔQ) and the d-band center (εd) of M-Ni2P on hydrogen adsorption free energy (ΔGH*) (M = Ti, Nb, V, Li, Cr, Na, Mn, Fe, Co, Sn, and Pb). Reproduced with permission from Ref. [167]. Copyright 2021, Elsevier.

Fig. 14. Temperature-dependent XRD patterns (a) and P 2s XPS spectra (b). Reproduced with permission from Ref. [174]. Copyright 2018, Springer Nature. HRTEM images (c) and corresponding FFT patterns (d) reveal the evolution of the degree of disorder. All scale bars represent 5 nm. (e) The DOS of the oxygen-incorporated MoS2 (top) and the pristine 2H-MoS2 (bottom). Reproduced with permission from Ref. [176]. Copyright 2021, John Wiley and Sons. (f) HRTEM image amorphous NiCo LDH. (g) LSV polarization curves for HER in 1 mol L-1 KOH. Reproduced with permission from Ref. [177]. Copyright 2020, Elsevier. (h) In situ XRD patterns for S-Co3O4/CC recorded during HER. (i,j) In situ Raman spectra of S-Co3O4/CC when the applied potentials shifted from -300 mV to increasingly positive potentials at low and high frequency range, respectively. (k) Co K-edge XANES spectra for S-Co3O4/CC recorded during HER. Reproduced with permission from Ref. [178]. Copyright 2024, John Wiley and Sons.

Fig. 15. (a) LSV curves measured in 1 mol L-1 KOH. (b) Summary of the overpotential at 10 mA cm-2 and exchange current density (j0). (c)TOF as a function of the calculated ΔGH. Reproduced with permission from Ref. [171]. Copyright 2020, John Wiley and Sons. (d) The HAADF-STEM image of Ru/Ni-MoS2. (e) The EXAFS fitting curves of Ni K-edge in Ru/Ni-MoS2 (insets: atomic structure model of Ru/Ni-MoS2). (f) Top view of the stable structure and charge density difference for the Ru atoms loaded on the MoS2 (left) without Ni and (right) with Ni. Reproduced with permission from Ref. [180]. Copyright 2021, Elsevier. (g) Atomic-resolution HAADF-STEM image and simulated image of the Co/Se co-doped MoS2. (h) The measured intensity profile along three lines labeled in (f). (i) HER polarization curves for Co/Se doped MoS2 samples. Reproduced with permission from Ref. [182]. Copyright 2020, Springer Nature.

Fig. 16. (a) Free energy vs. the reaction coordinates of MoS2 with various S-vacancy states. (b) STEM image and (c) electrochemical HER performance of S-deficient MoS2. Reproduced with permission from Ref. [94]. Copyright 2020, American Chemical Society. (d) Schematic illustration of layered molybdenum disulfide fabricated under various conditions. (e) Evolution of the S:Mo and Mo(UC):Mo(IV) ratios as a function of the annealing temperature of the electrodes. (f) Evolution of the Tafel slopes with the annealing temperatures and measured at pH ≈ 0 and pH ≈ 13. (g) Evolution of the TOF measured at 300 mV overpotential for 2H MoS2 and MoS2-xH and measured at pH ≈ 0 and pH ≈ 13. Reproduced with permission from Ref. [205]. Copyright 2019, American Chemical Society.

Fig. 17. (a) Dark-field scanning transmission electron microscopy image of SA-Ru-MoS2, where the red and green balls indicate Mo and S atoms, respectively. (b) 2D maps of electron density difference for single-atom Ru doping and S vacancy on the 2H/1T MoS2. (c) DOSs of pristine 2H-MoS2, 2H-Ru-MoS2-Sv, pristine 1T-MoS2 and 1T-Ru-MoS2-Sv. Reproduced with permission from Ref. [208]. Copyright 2019, John Wiley and Sons. (d) Free energy diagrams of the different MoS2 model catalysts under alkaline solution. (e) Schematic illustration for the electron transfer of Mo, C, and Co atom, and the valance band of β-Mo2C and Co50-Mo2C-12. (f) Relationship between specific activity at 180 mV and d-band center for β-Mo2C, Co50-Mo2C-4, Co50-Mo2C-12, and Co50-Mo2C-24. Charge density distribution of Co-Mo2C (g) and Co-Mo(v)-Mo2C (h). Reproduced with permission from Ref. [101]. Copyright 2019, John Wiley and Sons.

Fig. 18. (a) Schematic illustration of the formation of abundant O-vacancies induced by expanding the bond length of CoO nanorods. (b) Volcano plots of j0 measured in alkaline solution as a function of the ΔGH* for pure metals, Pt/C and CoO nanorods. (c) Electrocatalytic HER performance of CoO nanorods. Reproduced with permission from Ref. [219]. Copyright 2017, Springer Nature. (d) Schematic of the atomic structure for Ru@MoS2 with the changes of bond length. (e) The FT-EXAFS spectra of Ru/MoS2 before and after change the bond length. (f) Calculated PDOS of Ru/MoS2 before and after change the bond length. (g) Electrocatalytic HER performance. Reproduced with permission from Ref. [220]. Copyright 2021, Springer Nature.

Fig. 19. Current configurations of low-temperature water electrolyzers include alkaline (a), PEM (b), AEM (c) water electrolyzers. Reproduced with permission from Ref. [224]. Copyright 2022, John Wiley and Sons. (d) Polarization curves of the PEM electrolysers with P-CoSe2, M-CoSe1.28S0.72, and commercial Pt/C as cathode catalysts. (e) Chronopotentiometry curve of the PEM electrolyser operated at 1A cm-2 and 60 °C using M-CoSe1.28S0.72 and commercial IrO2 as cathode and anode, respectively. Reproduced with permission from Ref. [222]. Copyright 2023, AAAS. (f) Cell voltage versus current density plot of the AEM electrolyzer using γ-FeOOH-NS-NF as both anode and cathode and 10% Pt/C and IrO2 at room temperature. Reproduced with permission from Ref. [223]. Copyright 2024, American Chemical Society. (g) Photograph of the AEM electrolyzer performed in 1.0 mol L-1 KOH at 60 °C. (h) Current-voltage curves of AEMWE operated at different conditions. (i) Durability measurements of the AEM electrolyzer in 5.0 mol L-1 KOH at 60 °C. Reproduced with permission from Ref. [150]. Copyright 2023, Elsevier.

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