Research Progress on Mott-Schottky Hydrogen Evolution Catalysts Based on Metal/Transition Metal Compounds

doi:10.15541/jim20250124

Abstract

Abstract:

Hydrogen energy as an ideal energy carrier holds significant importance for promoting the transformation of energy structures. Electrolytic water splitting technology is crucial to achieve large-scale hydrogen production. The hydrogen evolution activity, stability and cost of catalysts are the key factors for its development. Transition metal compounds (TMCs) become popular candidates to replace noble-metal catalysts due to their low costs, abundant resources and tunable electronic structures. Mott-Schottky (M-S) junctions, constructed between transition metal compound semiconductors and metals, are considered to be an effective strategy to enhance catalytic activity. This review summarizes the research progress of metal/TMCs M-S junction catalysts, including their classification (metal/oxides, sulfides, selenides, phosphides, and nitrides, etc.), construction strategies (hydrothermal method, in-situ reduction, and phosphidation treatment, etc.), and enhancement mechanisms. Research findings indicate that the M-S junction optimizes their electronic structure and hydrogen adsorption free energy through interfacial charge rearrangement and their formation of built-in electric fields, thereby promoting charge separation and transfer and significantly enhancing hydrogen evolution activity. In addition, the review discusses the key issues that still need in-depth exploration and clarification regarding M-S junction catalysts, and provides an outlook on future research directions and development trends. It aims to offer theoretical guidance for design of efficient and cost-effective hydrogen evolution electrocatalysts and to promote sustainable development of hydrogen energy technology.

Key words: transition metal compound, Mott-Schottky junction, catalyst, hydrogen evolution reaction, review

CLC Number:

O646

REN Xianpei, LI Chao, HU Qiwei, XIANG Hui, PENG Yuehong. Research Progress on Mott-Schottky Hydrogen Evolution Catalysts Based on Metal/Transition Metal Compounds[J]. Journal of Inorganic Materials, 2026, 41(2): 137-149.

Figures/Tables 8

Fig. 1 Structures, types and enhanced hydrogen evolution mechanisms of metal/TMCs semiconductor M-S junction catalysts SEMI: semiconductor

Fig. 2 Preparation, characterization and hydrogen evolution performance of Ni-V2O3/PNF[37] (a) Schematic diagram of synthesis process for Ni-V2O3/PNF; (b) HRTEM image of Ni-V2O3/PNF; (c) Energy band diagram of Ni and V2O3;(d) Schematic diagram of band structures; (e, f) High-resolution XPS spectra of Ni2p (e) and V2p (f);(g) Linear sweep voltammetry (LSV) curves of 20% Pt/C, Ni-V2O3/PNF, Ni/PNF, V2O3/PNF, and Ni-V2O3/PNF-300/500, where 300 and 500 represent the thermal reduction temperatures in unit ℃, while 400 ℃ for Ni-V2O3/PNF

Fig. 3 Preparation, theoretical calculations and hydrogen evolution performance of Auδ+/1T-MoS1.76 and Mo-MoS2 M-S junction catalysts[44-45] (a) Schematic diagram of synthesis process for Auδ+/1T-MoS1.76[44]; (b) Schematic illustration of the energy band structure for Auδ+/1T-MoS1.76 heterostructure and the proposed charge-transfer mechanism[44]; (c) LSV curves and (d) linear fits of half capacitive current vs. scan rate for the extraction of Cdl for different samples[44]; (e) Free-energy diagram for HER[44]; (f) LDOS for different S sites of 2H MoS2 and Mo-2H MoS2[45]; (g) LDOS for different S sites of 1T MoS2 and Mo-1T MoS2[45]; (h) Optimal ΔGH* for HER[45]

Fig. 4 Theoretical calculations, band structure and hydrogen evolution performance of Mo@(2H-1T)-MoSe2 M-S junction catalyst[48] (a) Charge density distribution at interface of the Mo@(2H-1T)-MoSe2 heterostructure; (b) Electrostatic potential calculations of Mo metal (top) and MoSe2 (bottom); (c) Energy levels of the two components in Mo@(2H-1T)-MoSe2 before and after contact; (d) LSV curves and (e) corresponding Tafel slopes for the electrodes Mo mesh, Mo-MoSe2, Mo@(2H-1T)-MoSe2 and Pt/C in natural seawater; (f) LSV curves for Mo@(2H-1T)-MoSe2 before and after 1000 CV cycles

Fig. 5 Preparation, structure, band alignment and free energy of M-S type Co-Co2P@CNT//CM heterojunction[53] (a) Schematic diagram of synthesis process for M-S type Co-Co2P@CNT//CM heterojunction; (b) HRTEM and (c) SAED images of Co-Co2P@CNT//CM; (d, e) Energy diagrams for Co and Co2P before and after Schottky contact; (f) Calculated ΔGH* and (g) ΔEH2O of Co, Co2P and Co-Co2P

Fig. 6 Structural models, band structures and preparation schematic diagrams of Ni/W5N4 and Co-NC@W2N M-S junction catalysts[59-60] (a-c) Calculated geometries of (a) W5N4 (100), (b) Ni (111) and (c) M-S heterojunction[59]; (d) Structure diagram of atomic Bader charge coloring for the M-S heterojunction[59]; (e) Electrostatic potential for the corresponding geometries[59]; (f) Energy band diagram of metallic Ni and W5N4 with M-S interface after Schottky contact[59]; (g) HER polarization curves of the series of catalysts[59]; (h) Schematic illustration of Co-NC@W2N M-S junction after contacting[60]; (i) Schematic diagram of synthesis process for Co-NC@W2N[60]

Fig. 7 M-S junction formed between metallic compounds and TMCs semiconductors[62-69] (a) FeNi3/NiFe2O4[62]; (b) FeCoNi/MnWO4[63]; (c) Ni3S2/Fe3O4[64]; (d) Ni3S2/MoS2[65]; (e) NiS/MoS2[66]; (f) NiSe2/MoSe2[67]; (g) NiSe2/Ni2P[68]; (h) Co4N/Co2P[69]

Table 1 Summary of the direction of electron transfer in M-S junction catalysts

No.	Mott-Schottky catalyst	Metal	Semiconductor	Electron transfer	Ref.
1	V₂O₃/Ni	Ni	V₂O₃	Metal to semiconductor	[37]
2	Ni@NiO	Ni	NiO	Metal to semiconductor	[38]
3	Co/a-WO_x	Co	a-WO_x	Metal to semiconductor	[39]
4	Ni/NiFeO	Ni	NiFeO	Metal to semiconductor	[40]
5	Au/MoS₂	Au	MoS₂	Metal to semiconductor	[44]
6	Mo-MoS₂	Mo	MoS₂	Metal to semiconductor	[45]
7	Co-Co₂P	Co	Co₂P	Metal to semiconductor	[53]
8	NiCoP-Co	Co	NiCoP	Metal to semiconductor	[56]
9	Ni/W₅N₄	Ni	W₅N₄	Metal to semiconductor	[59]
10	Ni/Ni₃N	Ni	Ni₃N	Metal to semiconductor	[61]
11	FeNi₃/NiFe₂O₄	FeNi₃	NiFe₂O₄	Metal to semiconductor	[62]
12	FeCoNi/MnWO₄	FeCoNi	MnWO₄	Metal to semiconductor	[63]
13	Ni₃S₂/Fe₃O₄	Ni₃S₂	Fe₃O₄	Metal to semiconductor	[64]
14	Ni₃S₂/MoS₂	Ni₃S₂	MoS₂	Metal to semiconductor	[65]
15	Ru-WO_2.72	Ru	WO_2.72	Semiconductor to metal	[41]
16	Mo@(2H-1T)-MoSe₂	Mo	MoSe₂	Semiconductor to metal	[48]
17	Co/Co_0.85Se	Co	Co_0.85Se	Semiconductor to metal	[49]
18	Co/MoSe₂	Co	MoSe₂	Semiconductor to metal	[50]
19	Ru/Ru, Fe-CoP	Ru	Ru, Fe-CoP	Semiconductor to metal	[54]
20	Co/CoP	Co	CoP	Semiconductor to metal	[55]
21	Co-NC@W₂N	Co	W₂N	Semiconductor to metal	[60]
22	NiS/MoS₂	NiS	MoS₂	Semiconductor to metal	[66]
23	NiSe₂/MoSe₂	NiSe₂	MoSe₂	Semiconductor to metal	[67]
24	NiSe₂/Ni₂P	NiSe₂	Ni₂P	Semiconductor to metal	[68]
25	Co₄N/Co₂P	Co₄N	Co₂P	Semiconductor to metal	[69]

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