图1 金属/TMCs半导体M-S结催化剂的结构、类型以及增强析氢机制

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

图2 Ni-V2O3/PNF的制备、表征与析氢性能[37]

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

图3 Auδ+/1T-MoS1.76与Mo-MoS2 M-S结催化剂的制备、理论计算与析氢性能[44-45]

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]

图4 Mo@(2H-1T)-MoSe2 M-S结催化剂的理论计算、能带结构与析氢性能[48]

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

图5 M-S型Co-Co2P@CNT//CM异质结的制备、结构、能带与自由能[53]

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

图6 Ni/W5N4与Co-NC@W2N M-S结催化剂的结构模型、能带结构与制备示意图[59-60]

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]

图7 金属性质的化合物与TMCs半导体形成的M-S结[62-69]

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]