缺陷位工程在二维材料电催化析氢反应中的研究进展

doi:10.1016/S1872-2067(21)63945-1

摘要/Abstract

摘要：

面对不可再生资源的快速消耗和环境污染的日益加重, 寻找清洁可再生能源势在必行. 氢能是一种清洁可再生的能源, 是目前最有希望替代化石燃料的一种能源. 电化学水分解可用来产生高纯氢气, 其中析氢催化剂起着至关重要的作用. 尽管贵金属铂基催化剂表现出优异的析氢性能, 然而稀缺性和高成本限制了其大规模应用. 因此, 开发高效和地球存量丰富的电催化剂是实现大规模绿色能源转换和存储技术的关键.
二维材料可分为非金属材料(如石墨烯、碳化氮和黑磷)和过渡金属基材料(如卤化物、磷酸盐、氧化物、氢氧化物和碳氮金属化合物), 具有独特的结构和电化学性能, 为研究人员进行基础科学研究和新兴应用提供了广阔的空间. 对于未修饰的二维材料, 活性位点主要位于其边缘, 而大面积的基底化学活性非常低, 因此通常表现出较差的析氢活性. 但通过利用二维材料固有的物化性质(如大比表面积、缺陷位和功能化表面来微调现有催化位点或创建新的催化活性位点, 锚定其它活性物种构建复合材料), 可以对其进行设计以提高催化析氢反应活性. 随着二维材料的快速研发, 缺陷工程已成为构建高性能电催化剂制备的常用策略. 缺陷工程可以在二维材料中创建大量的边缘和孔, 并且在基底结构中创建空位进而产生了大量的活性位点.
本文主要讨论了缺陷的基本原理, 缺陷位点的构建方法(包括边缘缺陷、空位缺陷和掺杂衍生缺陷), 不同类型缺陷对析氢反应性能的影响, 缺陷位点上析氢反应机制以及提出了对二维材料缺陷的优化策略. 通过讨论缺陷结构与催化剂性能之间的关系, 为合理构建高性能的析氢催化剂提供了有益见解. 通过在不同位置构建缺陷位点, 调整局部电子结构形成不饱和配位态, 可以优化氢吸附/解离能. 最后, 提出了二维材料缺陷目前面临的问题和挑战, 并展望了二维材料缺陷在电催化析氢反应的未来发展趋势.

关键词: 缺陷位, 析氢反应, 氢吸附/解离能, 二维材料, 空位

Abstract:

The exploration of efficient and earth-rich electrocatalysts for electrochemical reactions is critical to the implementation of large-scale green energy conversion and storage techniques. Two-dimensional (2D) materials with distinctive structural and electrochemical properties provide fertile soil for researchers to harvest basic science and emerging applications, which can be divided into metal-free materials (such as graphene, carbon nitride and black phosphorus) and transition metal-based materials (such as halogenides, phosphates, oxides, hydroxides, and MXenes). For faultless 2D materials, they usually exhibit poor electrochemical hydrogen evolution reaction (HER) activity because only edge sites can be available while the base surface is chemically inactive. Defect engineering is an effective strategy to generate active sites in 2D materials for improving electrocatalytic activity. This review presents feasible design strategies for constructing defect sites (including edge defects, vacancy defects and dopant derived defects) in 2D materials to improve their HER performance. The essential relationships between defect structures and electrocatalytic HER performance are discussed in detail, providing valuable guidance for rationally fabricating efficient HER electrocatalysts. The hydrogen adsorption/desorption energy can be optimized by constructing defect sites at different locations and by adjusting the local electronic structure to form unsaturated coordination states for efficient HER.

Key words: Defect, Hydrogen evolution reaction, Hydrogen adsorption/desorption, energy, Two-dimensional material, Vacancy

唐甜蜜, 王振旅, 管景奇. 缺陷位工程在二维材料电催化析氢反应中的研究进展[J]. 催化学报, 2022, 43(3): 636-678.

Tianmi Tang, Zhenlu Wang, Jingqi Guan. A review of defect engineering in two-dimensional materials for electrocatalytic hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2022, 43(3): 636-678.

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图/表 38

Fig. 1. (A) Schematic of the procedure of plasma etching of graphene. (B) Device structure. (C) Schematic of the synthesis procedures. (D) The relation between formation energies and vacancy number. (E) Volcano curve of exchange current density i0 as a function of ΔGH*. (F) Structural vacancies and edge. (G) The relation between currents (log(i0)) and ΔGH*. (A,B) Reproduced with permission [22]. Copyright 2021, Wiley-VCH. (C) Reproduced with permission [23]. Copyright 2018, American Chemical Society. (D) Reproduced with permission [24]. Copyright 2013, American Physical Society. (E) Reproduced with permission [25]. Copyright 2020, American Chemical Society. (F) Reproduced with permission [26]. Copyright 2013, American Chemical Society. (G) Reproduced with permission [27]. Copyright 2015, Royal Society of Chemistry.

Fig. 2. Molecular structure diagram of graphene (A), BP (B), MoS2 (C), and MXene (D).

Fig. 3. (A) Graphical diagram for the preparation of Ru/MoS2/CP. SEM (B,C), HRTEM (D), HADDF-STEM (E) images and corresponding element mapping (F). (G) Polarization curves. (H) Comparison of the overpotentials. (I) Graphical diagram of interfacial cooperation between Ru and MoS2. Reproduced with permission [46]. Copyright 2017, Royal Society of Chemistry.

Fig. 4. (A) Schematic illustration of the preparation of cryo-mediated liquid phase exfoliation. (B) The formation mechanism of the defect-rich MoS2 NSs. Characterization of the d-MoS2 NS: (C) HRTEM image. (D) SAED pattern. (E) Identification of active sites/edges. (F) AFM image. (G) Height. (H) Schematic model structure. Reproduced with permission[48]. Copyright 2019, American Chemical Society.

Fig. 5. Point defect diagrams of vacancy (A), interstitial atom (B) and substitutional atom (C).

Fig. 6. Schematic diagram of two graphene edges.

Fig. 7. Atomic resolution STEM images (A) of TM-containing MoS2 with corresponding EELS (B). (C) HAADF-STEM image of VTi and two adjacent VTi within the same sublayer. (D) HAADF-STEM images of vacancy clusters. Scale bars are 0.5 nm. (E) VTi formation energy. (F) The relationship between formation energy of VTiC clusters and number of VTi. (G) HAADF image of DG. (A,B) Reproduced with permission [57]. Copyright 2020, Springer Nature. (C?F) Reproduced with permission [58]. Copyright 2016, American Chemical Society. (G) Reproduced with permission [60]. Copyright 2016, Wiley-VCH.

Fig. 8. (A) Typical Raman spectra of pristine graphene, DG and NG. Comparison of the intensity ratios I2D/IG (B) and ID'/IG (C) of DG and NG with the increase of ID/IG. (D,E) Raman spectra. (F) Raman position. XPS spectra of non-irradiated (G) and ion-irradiated (H) single layer MoS2. (A-C) Reproduced with permission [64]. Copyright 2013, Elsevier Ltd. (D) Reproduced with permission [65]. Copyright 2012, American Chemical Society. (E,F) Reproduced with permission [66]. Copyright 2019, American Chemical Society. (G,H) Reproduced with permission [69]. Copyright 2018, Royal Society of Chemistry.

Fig. 9. (A) Graphical representation for plasma modification of MoS2. (B) Schematic illustration for H2-plasma modification of MoS2 and AFM height images. (C) Graphical representation of the preparation of the Ni(OH)2/irradiated MoS2 heterostructure. (A) Reproduced with permission [43]. Copyright 2015, Royal Society of Chemistry. (B) Reproduced with permission [78]. Copyright 2016, Elsevier Ltd. (C) Reproduced with permission [84]. Copyright 2020, American Chemical Society.

Fig. 10. (A,B) ADF-STEM images of the MoS2 dendrites under lower magnification. (C) Atomic resolution ADF-STEM image with the corresponding FFT pattern as an inset. (D) Higher magnified image with the result after prolonged irradiation as an inset. The dendrite edges under lower magnification (E,G) and higher magnification (F,H) of the red and yellow boxed regions in panel (E,G), respectively. HRTEM images of MoSx-160 (I), MoSx-200 (J), MoSx-240 (K) and MoSx-260 (L). TEM image (M) and HRTEM image (N) of MoSx-220. (O) Observed defects in HRTEM image of MoSx-220. (P) HAADF-STEM image and corresponding EDS mapping images. (A?H) Reproduced with permission [87]. Copyright 2018, American Chemical Society. (I?P) Reproduced with permission [88]. Copyright 2020, Elsevier Ltd.

Fig. 11. (A) HADDF-STEM image of A-Ni@DG. (B) Enlarged image of the defective region (vacancy). (C) Enlarged image of the defective region with atomic Ni captured. (D) aNi@perfect hexagons. (E) aNi@D5775. (F) aNi@Di-vacancy. The projected densities of state (PDOS) with respect to perfect hexagons (G), D5775 (H), and Di-vacancy (I). (J,K) Energy profiles. Reproduced with permission [94]. Copyright 2018, Elsevier lnc.

Fig. 12. (A) Graphical representation for the synthesis of P-NSG. (B) Graphical representation for the preparation of SG-P on a plasma system. (C) Graphical representation for the experimental setup of inductively coupled plasma. (D) The contact measurement and the photo for contact behaviors of water droplets to pristine and H2 plasma treated a-MoSx. (E) XPS of the pristine a-MoSx. (F) XPS of the a-MoSx after H2 plasma treatment. (A) Reproduced with permission [101]. Copyright 2016, Elsevier Ltd. (B) Reproduced with permission [41]. Copyright 2016, Elsevier Ltd. (C?F) Reproduced with permission [102]. Copyright 2016, Wiley-VCH.

Fig. 13. (A) Synthesis processes of NSG nanosheets. (B) HAADF-STEM image of Cu@MoS2. (C) Filtered image of the orange square in (B). (D,E) Graphical representation of the formation mechanism of Cu@MoS2. (F) Schematic illustration of fabrication process of MoS2/NC. (G) Graphical representation of V-doped MoS2 nanosheets featuring interlayer. (H,I) HRTEM images of 10% V-MoS2 nanosheets. (A) Reproduced with permission [103]. Copyright 2020, American Chemical Society. (B-E) Reproduced with permission [105]. Copyright 2019, Elsevier B.V. (F) Reproduced with permission [106]. Copyright 2020, Elsevier Ltd. (H,I) Reproduced with permission [107]. Copyright 2020, Royal Society of Chemistry.

Fig. 14. (A) Synthetic diagram of SA-Ru-MoS2. (B) LSV curves. (C) Overpotentials at 10 mA cm-2. (D) Tafel plots. (E) Electrochemical impedance spectroscopy. Reproduced with permission [115]. Copyright 2019, Wiley-VCH.

Table 1 Various methods for constructing defect sites in 2D materials.

Construction method	Advantage	Disadvantage	Ref.
Plasma etching	controllable number of defects, easy to activate inert base	destructible original structure, difficult to operate	[41,56,102]
Hydrothermal synthesis	easy to synthesize, maintainable original crystal structure	uncontrollable concentration of defect	[107,108]
Chemical vapor deposition	easy to build the target structure, structural stability, easy to embedd dopant onto 2D materials, attainable single layer 2D materials with defects	uncontrollable concentration and type of defects	[72]
Thermal annealing	easy to synthesis	uncontrollable structure, easy to sintered; creating a large quantity of cracks and holes	[113]
Chemical etching	controllable concentration and distribution of defects	producing holes	[116]
Ion irradiation	controllable distribution of defects	difficult to operate	[55]

Fig. 15. (A) Cut infinite graphene sheets in different directions. (B,D) represent TEM images of SLG/FLG-DE. (C,E) represent AFM images. (F) Raman spectra. (G) I(D)/I(G) vs. FWHM(G) plot. (H) Statistical analysis of I(D)/I(D'). (I) XRD spectrum. (J) C 1s XPS spectrum. (K) Top view SEM image. (L,M) LSV curves. (N,O) The stability tests. (A) Reproduced with permission [123]. Copyright 2007, American Institute of Physics. (B?O) Reproduced with permission [114]. Copyright 2019, American Chemical Society.

Fig. 16. (A) The schematic diagram of the transfer. SEM images before and after the transfer of 780 (B?D) and 880 °C, (E?G). (H) Schematic diagram showing the edge of MoS2 for HER. Optimized surface model (top and side view) for hydrogen adsorption of MoO2 (I,J), MoS2 (K,L), MoS2/MoO2 (M,N). (O) ΔGH* for H adsorption. (P) curves LSV and Overpotential (Q) at various current densities. (R) Tafel slopes. (S) Nyquist diagram. (A?H) Reproduced with permission [125]. Copyright 2014, American Chemical Society. (I?S) Reproduced with permission [126]. Copyright 2020, Elsevier Ltd.

Fig. 17. (A) Two defect-free and defect-rich structure models. (B) TEM image of the defect-rich MoS2. (C,D) Correspond to the top and side views of HRTEM images of region 1 and 2 in (B). (E) Atomic reconstruction of (C) and (D). (F,G) The fresh edges inside the monolayer created by the oxygen plasma. (H) Raman spectra. (I) PL spectra. (J,K) STEM images. (L) Raman spectra. (M) PL spectra. (N) The overview of the composition process. LSV curves (O) and Tafel slopes (P). (Q) Double-layer capacitance (Cdl). (R) Durability test. (A?E). Reproduced with permission [127]. Copyright 2013, Wiley-VCH. (F?M) Reproduced with permission [56]. Copyright 2016, American Chemical Society. (N?R) Reproduced with permission [70]. Copyright 2018, Elsevier B.V.

Fig. 18. (A) HRTEM image of the monolayer MoS2. Atomic models represent the top view of a monolayer MoS2 with one (B) and three S (C) vacancies. (D) Polarization curves. (E) Tafel plots. (F) Nyquist plots. (G) Double-layer capacitance (Cdl). (H) Polarization curves before and after 1,000 cycles of continuous operation. (I) Stability test. Band structures of MoS2 with no S vacancies (J), one S vacancy (K), and two S vacancies (L). Charge density differences of monolayer MoS2 with one S vacancy (M) and two S vacancies (N). (A?I) Reproduced with permission [71]. Copyright 2016, Royal Society of Chemistry. (J?N) Reproduced with permission [111]. Copyright 2019, Royal Society of Chemistry.

Fig. 19. (A) Graphical representation of the construction of S vacancies in MoS2. (B) The relationship between surface free energy and potential. (C) Gibbs free energy. XPS spectra of Mo 3d (D) and S 2p (E) for MoS2/CoMoP2. (F) Raman spectrum. XPS spectra of Mo 3d peak (G) and S 2p peak (H) for the used MoS2/CoMoP2. (I) Raman spectrum of the used MoS2/CoMoP2. (J) Graphical representation of the function of S vacancies as localization and scattering centers for Raman vibration. (A?J) Reproduced with permission [146]. Copyright 2019, Elsevier B.V.

Fig. 20. (A) Graphical representation of the atomic structure of MoS2 with sulfur vacancies stabilized on defective graphene. Reaction free energy versus the reaction coordinate of HER for the line-shaped S-vacancies range of 0?12.5% supported on graphene with 0% (B), 1.85% (C), 3.70% (D), 5.56% (E), 11.11% (F) and 50% (G). The most stable adsorption positions for single H atom absorbing at VS (H), VS2 (I), VMoS3 (J), VMoS6 (K), MoS2 (L), MoS (M), Mo2S2 (N), S2Mo (O), SMo (P). (Q) Energetics of HER. (A?G) Reproduced with permission [158]. Copyright 2019, Elsevier Inc. (H?Q) Reproduced with permission [16]. Copyright 2016, American Chemical Society.

Fig. 21. (A?G) HAADF STEM images of MXenes after etching. 48% HF for 12 h (A?D) and 10% HF for 72 h (E?G). (H) Graphical representation of chemical etching. (I?K) Top view of HAADF-STEM of single W1.33C sheets. (L) HER polarization curves for different catalyst. (M) HER for different MXenes. (N) Onset potential for the HER on W1.33C before and after potential holds of 5 min at different cathodic potentials. (A?G) Reproduced with permission [162]. Copyright 2018, Wiley-VCH. (H?L) Reproduced with permission [163]. Copyright 2018, Wiley-VCH. (M?N) Reproduced with permission [164]. Copyright 2020, Wiley-VCH.

Fig. 22. (A) Schematic representation for the fabrication of B-SuG. (B-D) Typical TEM, HRTEM, and SEM images of NR-HGM-1000 and the corresponding C and N element maps. High-resolution XPS spectra (E) and N 1s XPS spectra (F) of the Nr-HGM samples obtained at 800, 900 and 1000 °C. Total nitrogen contents (G) and contents of different type nitrogen (H) of Nr-HGM samples. (I) HER polarization curves. (J) Comparison of the overpotential. (K) Tafel curves. (L) CV curves of the HT-AFNG at the various scan rates. (M) Scan rate dependent difference between anodic and cathodic currents at 0.32 V vs. RHE. (N) Polarization curves of the HT-AFNG. (O) Relative stability of -NH2 at different defect and edge sites. (P) ΔGH* for atomic H adsorption on different defects/edges on amine-functionalized and pristine NG. (Q) The calculated free-energy diagram. (R) Volcano curve of exchange current density. (S) The TDOS and PDOS for H adsorbed on the NH2 functionalized pyrrolic-N system. (A) Reproduced with permission [172]. Copyright 2014, Royal Society of Chemistry. (B-H) Reproduced with permission [186]. Copyright 2015, Elsevier Ltd. (M-S) Reproduced with permission [187]. Copyright 2018, Elsevier Ltd.

Fig. 23. (A) LSV curves. (B) Tafel plots. (C) LSV curves for N-MoS2-3. (D) Theoretical and experimental amount of hydrogen produced. (E) The free energy diagram. (F) DOS plots. (G) Partial charge density of single N-doped MoS2 monolayer. (H) PDOS plots of Mo 3d, S 2p and N 2p orbitals. (I) SEM of N-doped MoS2. (J) TEM image. (K) HRTEM image. (L) The corresponding EDS elemental mapping images. (M) Structural model. (N) ΔGH* of H* adsorption profile for various sites. (A-H) Reproduced with permission [62]. Copyright 2017, Wiley-VCH. (I-N) Reproduced with permission [192]. Copyright 2017, Elsevier B.V.

Fig. 24. (A) Schematic diagram of the synthesis of edge-enriched graphene. (B) Optical image and Raman mapping. (C) Raman spectra. (D) TEM image. (E) HR-TEM image of the graphene on a plane region. (F) HR-TEM image of the graphene on an edge region. (G) BF-STEM image and corresponding EELS elemental mappings. (H) Normal and distorted graphene edge model for calculation of total energy (eV). (I) TEM image; 3D bar plot of η10 vs pyN/gN ratio (J) and N/P ratio and corresponding contour plot (K). (A?H) Reproduced with permission [74]. Copyright 2019, Wiley-VCH. (I?K) Reproduced with permission [180]. Copyright 2020, American Chemical Society.

Fig. 25. (A) STEM image of BP(Co). (B) HAADF-STEM image and corresponding EDS elemental maps of BP(Co). (C) HAADF-STEM image of BP(Co). (D) XRD patterns of bulk BP and BP(Co). (E) P 2p XPS spectra. (F) Co 2p XPS spectrum of BP(Co). (G) Double-layer capacitances. (H) HER polarization curves. (I) Tafel plots. (J) LSV curves before and after 1000 continuous CV cycles. (K) Stability assessment. (L) EIS data. (M) Different charge density of H adsorbed at BP(Co) surface. (N) The ΔGH* values. (O) Dependence of ΔGH* on εLUS of the BP(metal). Reproduced with permission [167]. Copyright 2019, Wiley-VCH.

Fig. 26. (A) Synthesis of SMoS2 and TM-SMoS2. (B,C) HAADF-STEM images of Co-SMoS2. (D) Co at the Mo-atop site model and S vacancy site model. ADF (E) and EELS (F) acquired along the line in (B). (G) ADF intensity line profiles taken along the numbered lines 1 and 2 shown in (C). (H) HER polarization curves for different Co doping contents of mPF-MoS2 and 40% Pt/C. (I) Current densities at different overpotential. (J) Durability measurement. (K) Tafel plots. (L) The relationship between the Co doping content on S atom and the average ΔGH. (M) Schematic diagram of the bonding of H 1s and S 3p orbital. (N) Differential charge density. (O) ΔGH on S atoms versus the Bader charge of S atoms. (A-G) Reproduced with permission [209]. Copyright 2018, Royal Society of Chemistry. (H-O) Reproduced with permission [210]. Copyright 2017, Nature Portfolio.

Fig. 27. (A,C) TEM images of MoS2 nanosheets before and after Zn treatment. (B,D) HRTEM images. (E) MoS2 structure with 6.25% Zn vacancy and 18.75% S vacancy. (F) Vacancy formation energy of original MoS2 and 6.25% Zn doped MoS2. (G) The ΔGH values. (H) DOS. (I) Polarization curves. (J) Tafel plots. (K) TOF. (L) Stability test of Zn-MoS2 catalyst under acidic conditions. (A-I) Reproduced with permission [215]. Copyright 2019, Wiley-VCH. (J-L) Reproduced with permission [216]. Copyright 2017, American Chemical Society.

Fig. 28. (A,B) Atomic configurations of original and Nb-doped monolayer Ti3C2O2. (C) Atomic configuration of Co/Ni substituted Ti atom and Nb-doped monolayer Ti3C2O2. (D) ΔGH* of H* at the active sites of different monolayer Ti3C2O2. SEM (E), TEM (F), and HRTEM (G) images of Ni0.9Co0.1@NTM. (H) The inverse FFT of the selected region in (G). (I,J) The charge density difference between Ni-Cr2Co2 and Co-Cr2Co2. (K) The relationship between ΔGH* and H coverage. (L-O) The H adsorption sites with different structures of CV, OV, Pt-O and Pt-Mo defects. (P) Free energy curves of various defects. (A-H) reproduced with permission [220]. Copyright 2019, Wiley-VCH. (I-K) reproduced with permission [221]. Copyright 2018, Royal Society of Chemistry. (L-P) reproduced with permission [223]. Copyright 2019, American Institute of Physics.

Fig. 29. (A) FE-SEM image of VNMS. (B,C) TEM image. (D,E) IFFT pattern of the (002) plane. (F?H) IFFT pattern of the (100) plane. (I) SAED pattern. Mott-Schottky plot in both 0.5 M H2SO4 (J) and 1 M KOH (K). (L) Conduction and valence band behavior. (M) LSV measurements. (N) HER-overpotential comparison plot. (O) Tafel plots. (P) Chronopotentiometry stability test. (A?L) Reproduced with permission [228]. Copyright 2021, American Chemical Society (M?P) Reproduced with permission [229]. Copyright 2020, Royal Society of Chemistry.

Fig. 30. (A) BF-TEM image of monolayer MoS2 on Gr foils. (B) ADF-STEM image of MoS2. (C) TEM image. (D) FFT-filtered image of the region highlighted in panel (C). (E) BF-TEM image of MoS2 on Gr foils. (F) SAED pattern for panel (E). (G) Intensity line profile through the four diffraction spots circled in the dashed rectangle in panel (F). (H) ADF-STEM image. (I) Large-scale STM image. (J,K) Atomic-scale STM images of Gr. (L,M) Atomic-scale STM images of monolayer MoS2. Corresponding line profiles (N) and STS spectra (O) for MoS2/Gr, MoS2, and Gr on Au foils. Representative molecular dynamics snapshots of rectangular (P) and triangular (Q) MoS2 structures after 400 ps of the hydrogenation process. Evolution of the interaction of hydrogen atoms with rectangular (R) and triangular (S) MoS2 structures, with and without defects, during the MD simulation. Potential energy per atom of rectangular (T) and triangular (U) MoS2 structures with and without defects. Percentage of hydrogen that interacts with the surface and edges of rectangular (V) and triangular (W) MoS2 crystals. (A?O) Reproduced with permission [234]. Copyright 2016, Wiley-VCH. (P?W) Reproduced with permission [110]. Copyright 2020, American Chemical Society.

Fig. 31. (A) Mo appeared in the WS2-rich region. (B) W appeared in the MoS2-rich region. (C,D) Triangular domains of WS2 and MoS2. W-decorated MoS2 (E) and triangular vacancy (F). (G) Graphical representation for the preparation of MoS2/MoSe2. (H) TEM image of MoS2/MoSe2-0.5. (I) HRTEM image. (J) FFT pattern. (K) IFFT image. (L) HER mechanism on the MoS2/MoSe2. (A?F) Reproduced with permission [235]. Copyright 2017, American Chemical Society. (G?L) Reproduced with permission [236]. Copyright 2019, Royal Society of Chemistry.

Fig. 32. (A) Graphical representation for the preparation of Nb4N5-xOx-MoS2/NG. (B) SEM image. (C) TEM image. (D) STEM image. (E) STEM-EDX elemental mapping. (F) HAADF-STEM image. (G) Magnified HAADF image. (H) Graphical representation of covalently connected Nb4N5-xOx-MoS2 heterostructures. (I) HAADF-STEM image taken from the [001] direction of MoS2. (J) Magnified HAADF image from the boxed region in (I). (K) HAADF-STEM image taken from the [001] direction of Nb4N5-xOx. (L) Magnified HAADF image from the square boxed region in (K) and the graphical representation of Nb vacancy. (M) Magnified HAADF image from the boxed region in (K). (N) Chemisorption model of the H intermediate at S*, N*, and Nb* in the Nb4N5-MoS2 heterostructure. (O) PDOS. (P,Q) Free energies of H and water adsorbed. (A?Q) Reproduced with permission [241]. Copyright 2020, American Chemical Society.

Table 2 Comparison of HER performance on graphene-based catalysts in acidic media.

Catalyst	η@10 mA cm^-2 (mV)	Tafel slope (mV dec^-1)	Ref.
P-NSG	149	78	[101]
NS-doped graphene	-280	80.5	[68]
SLG/FLG-DE	55	61	[114]
A-Ni@DG	70	31	[94]
Ni@DG	84	44	[94]
(La-Gr)-graphene hybrids	279	112	[204]
(Yb-Gr)-graphene hybrids	363	147	[204]
(Eu-Gr)-graphene hybrids	160	52	[204]
PNG	379.73	125.5	[66]
PNG	338	88	[180]
G-NP	106	67.3	[67]
B-SuG	201	99	[172]
HT-AFNG	350	~113	[187]
N-VG	290	121	[189]
ACN-10%	-144	58	[188]
S-GNs	—	78	[177]
P-MoS₂/N,S-rGO	94	47.2	[242]
Co-NG	146	65	[226]
Co,N/3DG-2	141	97.3	[225]
MoS_1.7	143	39.5	[102]
MoS_3.1	206	84.2	[102]
Zn/defect-rich MoS₂/CC	—	55	[108]
10%V-MoS₂	146	48	[107]
DR-MoS₂ NW	95	78	[104]
Co-doped MoS₂	185	65	[72]
P-MoS₂/CC	131	48	[116]
MoS₂-irra2	177	66	[55]
Defective MoS₂ nanosheets	160	46	[70]
HDP MoS₂	385	109	[128]
MoS₂/MoO₂/MF	154	52.1	[126]
defective MoS₂ nanoflakes	214	52	[131]
MoS₂-5	190	54	[159]
Monolayer MoS₂	160	54.9	[71]
V_s-2H MoS₂	~176	~100	[243]
SV-MoS₂	-47	60	[157]
V-MoS₂/VGN@CP	128	50	[158]
P-MoS₂	43	34	[195]
Sn-MoS₂ nanosheets	28	37.2	[217]
N-MoS₂ QDs	165	51.2	[165]
N-doped a-MoS_x	143	57	[166]
N-doped MoS₂	168	40.5	[192]
N-MoS₂-3	35	41	[62]
mPF-Co-MoS₂-3.4	156	74	[210]
Co-doped MoS₂	218	50	[63]
Se-doped MoS₂	207	44	[63]
Zn@MoS₂	194	78	[215]
Cu-Pd-MoS₂	93	77	[219]
VNMS	51	36.44	[228]
NPC@MoS₂	178	58	[181]

Fig. 34. Unit cells (top) and band structures (bottom) of MoS2 (A), a 3 × 3 MoS2 cell with one S vacancy (B), a 3 × 3 MoS2 cell with a Pt atom on S vacancy (C), and a 3 × 3 MoS2 cell with one S vacancy and a Pt atom on MoS2 surface (D). Impact of S vacancy concentration on the band structure of MoS2 (upper) and hydrogen adsorption free energy (lower) for a 6 × 6 cell of MoS2 (E), a 6 × 6 cell of MoS2 with one S vacancy (F), and a 6 × 6 cell of MoS2 with 14 random S vacancies (G). Reproduced with permission [246]. Copyright 2017, Wiley-VCH.

Table 3 Comparison of HER performance on graphene-based catalysts and MoS2-based catalysts in alkaline media.

Catalyst	Electrolyte	η@10 mA cm^-2 (mV)	Tafel slope (mV dec^-1)	Ref.
Ni₂P@NSG	1.0 M KOH	110	43	[103]
Ru@GNs300	1.0 M KOH	40	28	[113]
ANSG	1.0 M KOH	-222	143.7	[42]
SLG/FLG-DE	1.0 M KOH	85	91	[114]
SHG	0.1 M KOH	-310	112	[182]
N-CoS₂/G	1.0 M KOH	-109	69.8	[200]
Ru/S-rGO	1.0 M KOH	—	38	[244]
SA-Ru-MoS₂	1.0 M KOH	76	21	[115]
MoS2/Ni	1.0 M NaOH	162	115	[130]
MoS2/CoMoP2	1.0 M KOH	75	80	[146]
Co-MoS₂/BCCF-21-1	1.0 M KOH	48	52	[211]
VNMS	1.0 M KOH	110	57	[228]
1T-Ni_0.2Mo_0.8S_1.8P_0.2 NS/CC	1.0 M KOH	55	66.1	[229]
1T-Ni_0.2Mo_0.8S_1.8P_0.2NFs	1.0 M KOH	99	72.3	[229]

Fig. 35. The optimal adsorption site (A) and the ΔGH of hydrogen adsorption (B) at different vacancy concentrations. The relationship between the calculated distance of H and Mo atoms and ΔGH is shown in (C). The configurations and band structures of O-doped defective SL-MoS2, 3.13% (D), 6.25% (E), 9.38% (F) and 12.50% (G). (H) The ΔGH on the O-doped defective SL-MoS2. (A?C) Reproduced with permission [247]. Copyright 2021, IOP Publishing Ltd. (D?H) Reproduced with permission [248]. Copyright 2021, IOP Publishing Ltd.

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