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Molybdenum Disulfide as an Electrocatalyst for Hydrogen Evolution Reaction

Yanmei Ren , Jiajun Wang , Ping Wang

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (8) : 1270 -1279.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (8) : 1270-1279 DOI: 10.7536/PC200770
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Molybdenum Disulfide as an Electrocatalyst for Hydrogen Evolution Reaction
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Abstract

Water splitting using the electricity from renewable energy sources offers a clean and sustainable way to produce H2 and meanwhile an advanced energy conversion technology. Thus it is expected to play a vital role in the future clean energy economy. Crucial to enabling this ideal vision is the development of high-performance and cost-effective electrocatalysts for the hydrogen evolution reaction(HER) and oxygen evolution reaction(OER). Molybdenum disulfide(MoS2) is a representative non-precious HER catalyst. A panoramic view of its researches and developments clearly shows that leading theoretical perspectives, logical material design, novel synthesis methods and advanced characterization technologies are the key components of a successful electrocatalyst implementation. At the same time, it also reflects the current research mode and points out the development directions of the electrocatalysts. This review covers a sequence of key discoveries and achievements that mark the development of MoS2 as a HER electrocatalyst, with special focuses on the implementation, effect and mechanism of the modification strategies including increasing the number of active edge sites, improvement of electrical conductivity and activation of inert basal planes. Finally, we briefly discuss the enlightenment from the studies of MoS2 electrocatalyst and look forward to the future trends of this appealing electrocatalytic material.

Contents

1 Introduction

2 Structure and properties of MoS2

3 The study of MoS2electrocatalyst for HER

3.1 Theoretical discovery and experimental verification of MoS2electrocatalysis for HER

3.2 The modification strategy to engineering active edge sites

3.3 The modification strategy to improving electrical conductivity

3.4 The modification strategy to activating basal planes

4 Several enlightenments from the studies of MoS2electrocatalyst

5 Conclusion and outlook

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Keywords

water splitting / hydrogen production / electrocatalyst / hydrogen evolution reaction / molybdenum disulfide

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Yanmei Ren, Jiajun Wang, Ping Wang. Molybdenum Disulfide as an Electrocatalyst for Hydrogen Evolution Reaction. Progress in Chemistry, 2021, 33(8): 1270-1279 DOI:10.7536/PC200770

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1 Introduction

Fossil energy is an important material basis for human modern civilization, but today, fossil energy has increasingly become the source of problems restricting the sustainable development of human society. On the one hand, fossil energy resources are becoming increasingly scarce, causing serious energy security problems; On the other hand, environmental pollution and climate change caused by the long-term use of fossil fuels seriously threaten the living environment of human beings[1]. The development and utilization of clean and renewable energy has become the only way to fundamentally solve global problems such as energy and environment. Hydrogen is a clean and efficient secondary energy carrier, which is expected to play an important role in the future clean energy economy. However, the realization of large-scale application of hydrogen energy requires the construction of a complete hydrogen energy industry chain including hydrogen production, hydrogen storage and hydrogen use, each of which is facing severe technical challenges[2,3]. For hydrogen production, the existing mainstream hydrogen production technologies, such as natural gas reforming, petroleum gasification and coal gasification, rely heavily on fossil fuels and do not have sustainable development attributes. Water electrolysis is a clean hydrogen production technology, but its scale is limited due to the high cost of hydrogen production, which currently accounts for only about 4% of the total hydrogen production[4]. However, with the development and application of renewable energy technology, this situation will be fundamentally changed. Water is an ideal raw material for hydrogen production because of its abundant reserves and wide sources in nature. The decomposition of water by electric energy generated by primary renewable energy such as solar energy, wind energy and tidal energy can provide a clean and convenient way to produce hydrogen and fundamentally get rid of fossil fuel dependence. At the same time, the conversion of primary energy to chemical energy with electric energy as the medium can effectively solve the inherent intermittent and regional problems of primary energy, and provide a feasible scheme for improving the efficiency of primary energy utilization[5]. In this way, the coupling utilization of electrolyzed water and primary renewable energy will promote the development of hydrogen energy technology and renewable energy conversion and application technology.
Hydrogen evolution reaction (HER) and Oxygen evolution reaction (OER) are involved in water electrolysis. The development of highly active electrocatalysts to reduce the overpotential of the two half-reactions to improve energy efficiency is the core research content of water electrolysis technology. For HER, the noble metal Pt is recognized as a highly active catalyst, but its high material cost and resource scarcity seriously restrict its practical application. Over the past decades, scholars from various countries have actively explored non-noble metal HER catalysts, and made positive progress in discovering new catalytic materials and expanding the scope of material research. At present, a wide variety and a large number of HER catalytic materials have been formed.According to the material category, the catalyst can be divided into four types: transition metal, alloy, metal compound and non-metal material, among which the metal compound catalyst includes sulfide, phosphide, nitride, carbide, boride and oxide[6⇓~8][9⇓~11][12⇓~14][15⇓~17][18⇓~20][21⇓~23]. Thanks to the progress of material preparation and characterization technology and the improvement of computing power, non-noble metal HER catalysts have made great progress in material composition design, nanostructure control and modification mechanism analysis. At present, a variety of Ni-based alloys or compounds have shown similar HER catalytic activity to that of noble metal Pt, which preliminarily confirms the feasibility of obtaining high-performance and low-cost HER catalysts[24⇓~26].
Although different types of catalysts have different intrinsic activity, conductivity or material structure characteristics, there are many similarities in the design of electrocatalytic materials, modification strategies and composition/structure modulation methods. In this case, it is of great benefit to select representative HER catalysts and clarify their development history, research ideas, modification effects and mechanisms, so as to accurately grasp the research trends and development trends of HER catalysts with complex systems. In This paper, the development of electrocatalysts for hydrogen evolution in MoS2 is reviewed in chronological order of the important discoveries and advances of molybdenum disulfide (Molybdenum disulfide,MoS2).The implementation methods, effects and mechanisms of modification strategies, such as increasing edge active sites, improving conductivity and constructing basal surface active sites, were discussed.Finally, the research enlightenment of MoS2 hydrogen evolution electrocatalysts was summarized from the global perspective of the field, and its future development trend was prospected.

2 Structure and Physicochemical Properties of Molybdenum Disulfide

Molybdenum disulfide (MoS2) is a typical layered transition metal compound, which is composed of MoS2 with sandwich structure stacked by van der Waals forces. In the MoS2 monolayer, the Mo atom layer is located between two S atom layers, and the Mo and S atoms are covalently bonded[28,29]. In terms of chemical properties, MoS2 is relatively stable, not easy to oxidize, insoluble in water, dilute acid, concentrated sulfuric acid, alkali and organic solvents, but soluble in boiling concentrated sulfuric acid and aqua regia. The valence bond structure of the MoS2 determines its anisotropic characteristics. In terms of electrical properties, the intralayer conductivity is more than two orders of magnitude higher than the interlayer conductivity[27,28]. In the aspect of mechanical properties, the external force is easy to cause the MoS2 to peel off and form a two-dimensional sheet structure; In addition, due to the weak interlayer interaction, the MoS2 is also easy to be chemically exfoliated by inserting foreign ions between the layers[28,30].
According to the arrangement of atoms and the stacking order of the lamellae, the bulk MoS2 exhibit a variety of crystal structure types, such as 2H, 3R, 1T, 1T 'and 1T ″ (H, R and T stand for hexagonal, orthorhombic and rhombohedral structures, respectively; The number represents the number of MoS2 monolayers per unit cell). In the three common crystal forms of 2H, 3R and 1T (as shown in Figure 1), 2H is a thermodynamically stable phase, and its structural unit is a S-Mo-S monolayer with two layers of AB type stacking, and the Mo atom is in a triangular prism coordination. The structural units of 3R and 1T are S-Mo-S monolayer and S-Mo-S monolayer with three-layer ABC-type stacking, respectively, in which the Mo atoms are trigonal and octahedral, respectively. Both 3R and 1T are metastable phases, which can be transformed into 2H phase under heating or microwave irradiation[29,31,32]. For a single layer of MoS2,S, the arrangement of atomic layers determines that there are two possible crystal forms, 2H and 1T, which can be transformed into each other through the lateral sliding of S atomic layers. The change of the symmetry of the crystal structure and the coordination environment of Mo atoms results in the change of the electronic properties of the MoS2, for example, 2H and 3R phases have semiconducting properties, while 1T phase has metallic properties[33⇓~35].

3 Studies on molybdenum disulfide electrocatalyst for hydrogen evolution reaction

3.1 Theoretical discovery and experimental verification of hydrogen evolution activity of MoS2;

Studies on the electrocatalytic activity of mV vs RHE for hydrogen evolution can be traced back to the 1970s, when it was found that the onset potential of mV vs RHE for hydrogen evolution was about -90 mV vs RHE (relative to a reversible hydrogen electrode), and the Tafel slope was as high as 692 mV·dec-1[36]. Because of its poor catalytic activity, MoS2 has not been paid attention to by researchers for quite a long time. Until 2005, Nørskov and others reported subversive theoretical research findings that changed the situation[37]. Density functional theory (DFT) calculations show that the hydrogen adsorption free energy (ΔGH*) of Mo sites on the MoS2(100) surface is as high as 1. 92 eV, while the ΔGH* of Mo sites on the edge is only 0. 08 eV, which is close to the hydrogen adsorption free energy (ΔGH*=-0.09 eV) of Pt. The calculation results not only explain the poor electrocatalytic activity of bulk MoS2 for hydrogen evolution, but also predict for the first time that the unsaturated coordinated Mo atoms at the edge of MoS2 particles are the active sites of HER.Therefore, it is speculated that nanostructured MoS2 is expected to become a highly active HER catalyst.
The theoretical prediction of Nørskov et al. Has been confirmed by experiments. Chorkendorff et al. Deposited MoS2 nanoparticles on the surface of Au (111) substrate by physical vapor deposition, and then measured the area and edge length of MoS2 nanoparticles by scanning tunneling microscopy (STM), and then studied the correlation between the area and edge length of MoS2 nanoparticles and their photocatalytic activity[38]. The results (Figure 2) show that the HER-catalytic activity of the MoS2 is linearly related to the edge length of the sample particles and is independent of the area, which confirms that the edge of the MoS2 nanoparticles provides HER-active sites, thus starting the research boom of MoS2 hydrogen evolution electrocatalysts (Table 1).

3.2 Increasing marginal active sites of modification strategies

After confirming that the unsaturated coordination Mo atom is the active site of the MoS2, structural regulation to increase the number of active sites naturally becomes the preferred strategy for the modification of the MoS2. Thanks to the rapid development of preparation and characterization technology of nanomaterials, scholars from all over the world have made gratifying progress in nano-scale control of MoS2, which is first reflected in the successful synthesis of low-dimensional MoS2 materials. Wilkinson et al., using MoO3 and sulfur (S) powder as starting materials, prepared MoS2 nanosheets with high edge/basal plane ratio by ball milling combined with high temperature heat treatment. Due to the high density of edge active sites, the HER activity of this material is much higher than that of bulk materials (as shown in Figure 3a-c)[39]. Yang et al. Grown one-dimensional single crystal MoS2 nanoribbon array on the surface of n-type Si substrate by chemical vapor deposition method. Because the (001) plane of the MoS2 nanoribbon is perpendicular to the substrate, the exposed surface of its top is all edge active sites[40]. When the nanoribbon material is used for catalyzing hydrogen peroxide, the overpotential required for reaching the 20 mA·cm-2 current density is 170 mV, which is obviously superior to that of a two-dimensional single-layer MoS2 material. Gopalakrishnan et al. modified MoS2 quantum dots on MoS2 few-layer nanosheets by an improved liquid phase stripping method, and greatly increased the density of active sites by constructing this heterodimensional nanostructure, thus significantly reducing the onset potential of HER[41]. In addition, Xu et al. Synthesized zero-dimensional MoS2 quantum dots with an average particle size of about 3 nm by combining ultrasound and solvothermal method, and compared with the reference sample, which also confirmed the important influence of the number of active sites on HER activity[42].
The results show that the number of unsaturated coordinated Mo atoms can also be increased by controlling the synthesis of MoS2 with specific morphology or defect structure by nano-engineering strategy, thus improving the catalytic activity. Using ultrathin Mo film (about 5 nm in thickness) and S powder prepared by electron beam evaporation as raw materials, Cui et al. Grown MoS2 lamellar arrays perpendicular to the substrate on glassy carbon substrate by rapid vulcanization method, which had abundant edge active sites.Its exchange current density is about one order of magnitude higher than that of MoS2 nanoparticles (as shown in Figure 3G ~ I); Ye et al. Introduced cracks and holes in the MoS2 sheet by oxygen plasma etching and high temperature reduction heat treatment, respectively, to increase the number of unsaturated coordination atoms[43][55]. It was found that, compared with oxygen plasma etching, the effect of introducing defects by reducing heat treatment was better, so the prepared samples had more excellent HER-activity (as shown in Figure 3d-f). Compared with the above work, Jaramillo et al. 'S work on nanoscale morphology control of MoS2 is more creative. They successfully synthesized 3D large-scale MoS2 films with double helix morphology and mesoporous structure by combining hard template method, evaporation-induced self-assembly, electrodeposition and vulcanization[6]. The construction of high curvature surface and 3D porous structure endow the material with abundant edge active sites. However, due to the poor conductivity of the materials, the hydrogen evolution overpotential of the novel MoS2 catalyst is still as high as 220 mV (corresponding to the 10 mA·cm-2 current density).
While focusing on the active site of Mo, the catalytic function of S site has gradually entered the field of vision of researchers. Among the large number of edge sites exposed in the MoS2 catalyst, S occupies a large proportion, and if S can be endowed with catalytic function, the catalytic activity of the MoS2 catalyst can be further improved[56,57]. Chorkendorff et al. Found that doping Co atoms into the MoS2 lattice can greatly reduce the ΔGH* of S edge sites (from 0.18 eV to 0.10 eV), which is close to the ΔGH*(0.08 eV) of Mo edge sites[57]. However, up to now, there are few experimental reports on the successful construction of Mo/S double edge active sites, and its feasibility remains to be confirmed.

3.3 Lectrical conductivity enhancement by modification strategy

According to the theoretical prediction, the intrinsic activity of MoS2 under acidic conditions is comparable to that of noble metal Pt, but the measured apparent activity is much lower than that of Pt[37]. The reason is that the poor conductivity of MoS2 is an important factor restricting its electrocatalytic performance. If the problems of the number of active sites and conductivity can be solved at the same time, the electrocatalytic performance of MoS2 is expected to be greatly improved. To solve this problem, researchers from various countries have proposed a variety of solutions, such as conductive substrate composite, heteroatom doping, crystal control and structure regulation.
It is a common strategy to combine electrocatalytic materials with conductive substrates to improve the conductivity of electrocatalysts. In the choice of conductive matrix, carbon materials become the first choice because of its good conductivity and excellent chemical stability. Dai et al. Used a simple solvothermal method to grow highly dispersed MoS2 nanoparticles on reduced graphene oxide (RGO) (as shown in Figure 4A). Thanks to the construction of the RGO conductive network and the good electrical contact between the RGO and the MoS2 nanoparticles, the composite electrocatalyst has fast electron transport properties[44]. At the same time, the introduction of RGO substrate can effectively avoid the agglomeration of MoS2 nanoparticles, thus exposing more edge active sites. As a result, the MoS2/RGO composite electrocatalyst exhibits excellent electrocatalytic performance, with an overpotential of only 150 mV at 10 mA·cm-2 and a Tafel slope of about 41 mV·dec-1 (as shown in figs. 4 (B) and (C)). In addition, porous carbon, carbon nanotubes, carbon cloth and other carbon materials have been widely used in the modification of MoS2 catalysts, and have achieved good catalytic activity improvement[58][59][60]. In addition to carbon materials, the introduction of other highly conductive substrates can also effectively improve the catalytic activity of MoS2 catalysts[45,61,62]. Chen et al. used the method of pre-deposition MoO2 combined with subsequent vulcanization to grow MoO2@MoS2 composite catalysts with core-shell structure on the surface of carbon cloth (as shown in Figure 4D)[45]. It was found that the control of sulfidation conditions was the key to optimize the activity of MoS2, and too low sulfidation degree led to insufficient generation of active phase of MoS2. Over-sulfidation leads to a large consumption of MoO2, which affects the conductivity and HER activity of the catalyst, thus highlighting the important role of the conductive matrix in the catalysis of HER by MoS2 (as shown in Figure 4 e, f).
Heteroatom doping is also an effective method to improve the conductivity of MoS2, and its intrinsic mechanism is to modify the electronic structure of MoS2. The theoretical study of Xie et al shows that the introduction of O atoms into the MoS2 lattice can enhance the hybridization between the d orbital of Mo and the p orbital of S, which leads to the narrowing of the energy band gap of the MoS2 and the improvement of its conductivity[46]. Bollinger et al. Found that the edge sites of the MoS2 have good conductivity, which is much higher than the conductivity of the base surface[63]. Inspired by this, Xiao et al. Considered that improving the conductivity of the MoS2 surface by atom doping is one of the important ways to improve the catalytic activity of HER[47]. It is found that the doping of N atoms into the base plane of the MoS2 can increase the Mo 3d-S 2p-N 2p hybridization near the Fermi level and induce the uniform distribution of charges on the base plane, thus improving the conductivity of the base plane.This is preliminarily confirmed by the experimental results.
While paying attention to the conductivity of the substrate, improving the electron transition efficiency between the layers of the MoS2 is also an optional way to modify the electrocatalyst of the MoS2. The basal plane conductivity of the MoS2 is much higher than the interlayer conductivity, and researchers pay more attention to the former and ignore the latter[28,27]. In this regard, Yu et al. Put forward different views[64]. They used chemical vapor deposition (CVD) method to prepare a few layers of MoS2, and achieved precise control of the number of layers by controlling the amount of precursors. It was found that the hydrogen evolution activity of the MoS2 was significantly dependent on the number of layers, and the hydrogen evolution activity decreased by about 4. 47 times with the increase of one MoS2 layer. They believe that this performance-layer number correlation is due to the electronic transition between layers, so improving the efficiency of electronic transition between layers is the key to improving the hydrogen evolution activity of MoS2, which can be achieved by intercalation of metal atoms or ions (Fig. 4G).
The abundant crystal structure of MoS2 also provides a modification space for improving conductivity and even enhancing electrocatalytic performance[33⇓~35]. The 1T phase with metallic properties is clearly more suitable for use as an electrocatalyst than the 2H phase with semiconducting properties, which has been confirmed by experiments. Voiry et al. Systematically compared the photocatalytic activity of 2H-MoS2 and 1T-MoS2[65]. The results showed that the 1T-MoS2 exhibited higher HER-catalytic performance, and the overpotential at 10 mA·cm-2 current density was about 100 mV lower than that of the 2H-MoS2 (as shown in Fig. 4 H, I). On the one hand, the good metal conductivity of 1 T phase accelerates the charge transfer rate in the reaction process, on the other hand, more active sites on the basal surface of 1 T phase increase the number of reaction sites. However, it seems that it is difficult to synthesize the 1T-MoS2 directly by conventional methods.Previously, researchers mostly used the phase transformation method to obtain the 1 T phase, that is, using the thermodynamically stable 2 H phase as the precursor, and using ion intercalation, element doping, electron beam scanning and mechanical strain to promote the transformation to the 1 T phase[30][66][35][67]. Lukowski et al. prepared 1T-MoS2 nanosheets by lithium intercalation chemical exfoliation method. Under the condition of not realizing the complete transformation of 2H → 1T phase, the catalyst showed excellent photocatalytic activity, and the hydrogen evolution overpotential was 187 mV(10 mA·cm-2 current density).Deng et al. utilized the synergistic effect of N-doping and PO43- intercalation to promote the transition from 2H to 1T phase of MoS2, and introduced the carbon cloth matrix with surface-modified graphene nanosheets to improve the specific surface area and conductivity[30][48]. Although the phase transformation rate is only 41%, the hydrogen evolution overpotential of the prepared catalyst is only 85 mV(10 mA·cm-2 current density), and the Tafel slope is about 42 mV·dec-1. They believe that the simultaneous introduction of N and PO43- can induce the phase transition of MoS2, adjust the electronic structure of the catalytic active phase, and reduce the hydrogen adsorption free energy of the active site, that is, the main reason for the excellent performance of the catalyst lies in the improvement of intrinsic activity and conductivity. Recently, important progress has been made in the synthesis of 1T-MoS2, and researchers have synthesized high-purity 1T-MoS2 by hydrothermal and sonochemical-assisted reduction methods[49][68]. These achievements will undoubtedly promote the research of MoS2 hydrogen evolution electrocatalysts, but the stability problems caused by the nature of metastable phase still make their application face challenges.

3.4 Active site of that construction substrate of the modification strategy

For MoS2 hydrogen evolution electrocatalytic materials, the edge active sites are well known, while the dominant basal atoms are catalytically inert (ΔGH*≈1.92 eV)[37]. If we can increase the number of edge active sites and improve the conductivity of the catalyst, at the same time, we can take effective methods to activate the basal atoms to make them have catalytic activity, which is expected to greatly improve the photocatalytic activity of MoS2.
Using surface defect engineering strategy to construct active sites on the substrate is a new way to develop high-performance MoS2 electrocatalysts. In 2016, Nørskov and Zheng took the lead in revealing the feasibility of this approach from theoretical and experimental perspectives[50]. It is found that the introduction of S vacancy into the MoS2 lattice can lead to the formation of a new local electronic state in the energy gap near the Fermi level, which leads to the direct adsorption of H on the adjacent Mo atom, and the strength of H adsorption increases with the increase of the number of S vacancy. In this way, the introduction of basal S vacancies will become an integrated method to construct active sites and optimize their activity.
In the verification experiment, they used wet chemical method to transfer the single-layer 2H-MoS2 prepared by CVD method to the gold nanocone, and generated tensile strain in the MoS2 film through capillary force. The S vacancy was introduced into the basal plane of the MoS2 by Ar plasma etching. The test results show that the introduction of S vacancy can construct highly active sites. The use of elastic strain alone can only improve the catalytic activity, while the combination of elastic strain and elastic strain can significantly improve the catalytic activity. This work quickly aroused the interest of scholars around the world in the study of the defect structure of the MoS2, and then a variety of simple S-vacancy introduction methods were reported one after another[51,69]. However, due to the high input energy and the uncontrollable processing kinetics, the traditional method is easy to form multi-dimensional defects such as holes and cracks while introducing vacancies, which makes it difficult to accurately evaluate the modification effect of vacancies. To solve this problem, Zhang et al. proposed a simple H2O2 chemical etching method (as shown in Figure 5A), and realized precise regulation and control of the concentration and distribution of single-atom S vacancies on the MoS2 basal plane by changing the etching time, temperature, etchant concentration and other conditions, which provided a material and method basis for in-depth study of the modification effect and mechanism of S vacancies[52]. The results show that the electron delocalization of the Mo atoms near the S vacancy is the key to activate the active site of HER. At the same time, electron delocalization also brings the added benefit of improved conductivity. By optimizing the preparation conditions, the concentration of monatomic S vacancy in the basal plane of the MoS2 can be increased to 12. 11%, which is close to the theoretical prediction value of 12. 50%.The hydrogen evolution overpotential of the MoS2 at 10 mA·cm-2 is only 131 mV, and the Tafel slope is about 48 mV·dec-1.
Inspired by the theory that S vacancy defects activate the inert basal planes of MoS2, Wang et al. Studied the electronic structure and HER-catalytic behavior of 16 structural defects (vacancies, grain boundaries, etc.) Through first-principles theoretical calculations[70]. The calculated results show that all of the six structural defects may be the active sites of HER. He et al. Synthesized MoS2 films with ultra-high grain boundary density by Au quantum dot-assisted vapor deposition method, and proved that grain boundary structural defects can provide HER-catalytic active sites (as shown in Fig. 5 B ~ d)[71]. Zhu et al. Found that the 2H-2H domain boundary and 2H-1T phase boundary of the MoS2 have the function of HER-catalysis[53]. Through the multi-level domain boundary/phase boundary design, the single-layer MoS2 only needs 136 mV of hydrogen evolution overpotential to reach the 10 mA·cm-2 current density (as shown in Fig. 5e ~ G), and no significant performance degradation is observed in the 200 H acid condition durability test. In addition, impurity atoms can also serve as effective HER reaction sites. Tapaszt Tapaszt et al. Obtained MoS2-XOx replacement solid solution with high crystallinity by ambient spontaneous oxidation of MoS2, and observed that oxidation led to the improvement of material activity[72]. They believe that the substitution of O atoms and the higher electronegativity of O atoms enhance the ability of H adsorption on O active sites, which makes it show considerable catalytic activity.

4 Some Inspirations from the Study of Electrocatalysts for Hydrogen Evolution in MoS2;

(1) Throughout the research history of hydrogen evolution electrocatalysts in MoS2, theoretical calculations have played a vital role in leading and promoting. From the theoretical prediction of defect active sites to the improvement of conductivity by heteroatom doping to the activation of inert substrates, theoretical calculations are leading the experimental research in the right direction. On the other hand, the theoretical analysis of the electrocatalytic modification mechanism of MoS2 also provides the premise and basis for optimizing the design of material composition, and promotes the improvement of material research efficiency and the transformation of research type from "experiential" to "design".
(2) The progress of material preparation and characterization technology has strongly promoted the research and development of electrocatalytic materials. Thanks to the rapid development of nanomaterial preparation technology, a large number of MoS2 materials with low-dimensional or novel structures have been successfully synthesized, and the fine control of the composition or defect structure of materials at the atomic scale has become a reality, which opens up a broad space for the modification of electrocatalysts. At the same time, the application of advanced characterization technologies, such as electron microscopy, synchrotron radiation and in-situ characterization, provides a practical feasibility for obtaining atomic-scale composition and structure information of materials and exploring the intrinsic relationship among surface composition/configuration, electronic structure and apparent catalytic performance.
(3) Synergistic modification of multiple factors is the key to the development of highly active electrocatalysts[48,54,62,73,74]. Intrinsic activity, number of active sites and electrical conductivity are the three factors affecting the electrocatalytic performance, and it is usually difficult to substantially improve the apparent performance of the catalyst by simply solving one of the problems. In the research of the optimal design and controllable synthesis of MoS2 electrocatalysts, the modification strategies such as increasing edge active sites, improving the conductivity of materials and constructing active sites on the substrate should be used comprehensively, and the multi-factor synergistic modification should be achieved through simple and easy preparation methods.

5 Conclusion and prospect

MoS2 is the most intensively studied non-noble metal hydrogen evolution electrocatalytic materials.Throughout its research history, the exploration of modification methods under the guidance of mechanism understanding has always occupied a dominant position, and the application of this "rational research" mode reflects the mainstream trend of future catalyst research and new material development from one side. In the research of MoS2 hydrogen evolution electrocatalysts, many modification strategies, such as nanostructure modulation, heteroatom doping, defect engineering and phase structure control, have been used to increase the edge active sites, improve the conductivity and construct the active sites on the substrate, which effectively improve the electrocatalytic activity of the materials. However, from the practical point of view, MoS2 hydrogen evolution electrocatalysts still have the following problems to be solved urgently:
(1)1T-MoS2 have high intrinsic activity and good conductivity, and the synthesis of their materials has also made positive progress. However, the nature of thermodynamic metastable phase results in the inherent disadvantage of structural instability of 1 T phase, and how to improve the stability of 1 T phase under long-term electrochemical operation conditions is the key to determine its practicability.
(2) Fine control of surface composition and defect structure at atomic scale is the main way to improve the intrinsic activity and conductivity of MoS2 electrocatalysts. At present, the research in this area is still in its infancy, and whether a simple and easy fine control technology can be developed is another key factor to determine the practicability of MoS2 electrocatalysts.
(3) The application of existing modification methods has substantially improved the photocatalytic performance of MoS2, but it is still far lower than that of noble metal Pt. In view of the inherent shortcomings of MoS2, such as poor surface site activity and low interlayer conductivity, and the limited space for composition/structure modification of single-phase materials, the construction of MoS2 based multiphase composite electrocatalytic materials may be the mainstream trend in the future.

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Funding

National Key R&D Program of China(2018YFB1502104)

Foundation for Innovative Research Groups of the National Natural Science Foundation of China(51621001)

Natural Science Foundation of Guangdong Province(2016A030312011)

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