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Application of POMs-Based Sulfided Catalyst in Hydrodesulfurization and Hydrogen Evolution by Electrolysis of Water

Changle Yue , Wenjing Bao , Jilei Liang , Yunqi Liu , Daofeng Sun , Yukun Lu

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (5) : 1061 -1075.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (5) : 1061-1075 DOI: 10.7536/PC210608
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Application of POMs-Based Sulfided Catalyst in Hydrodesulfurization and Hydrogen Evolution by Electrolysis of Water
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Abstract

Facing the challenge of severe environmental pollution caused by petroleum and the development of new energy, the desulfurization of petroleum fuels and sustainable clean alternative energy are regarded as important solutions. As a clean and sustainable energy carrier, hydrogen (H2) is considered one of the most promising alternatives to carbon fuels. Therefore, hydrodesulfurization (HDS) and electrolysis of hydrogen evolution reaction (HER) are effective ways to solve the current energy and environmental problems caused by petroleum, and the development of high-efficiency and low-cost non-precious metal-based catalytic materials is a key step to achieve industrialization. Sulfided transition metals have high valence, unique crystal structure and thermal stability. Among them, MoS2 and WS2 are a type of band gap two-dimensional semiconductors with high planar carrier mobility and are used as non-noble metal sulfided catalysts representative material. It is worth noting that MoS2 and WS2 can realize HDS and HER processes at the same time. They not only serve as high-performance HDS catalysts to reduce the sulfur content of petroleum, but also shine in sustainable and clean green hydrogen production. Polyoxometalates (POMs), as a kind of inorganic nanoclusters with a clear structure composed of a variety of transition metals and oxygen atoms, are suitable precursors for preparing transition metal sulfided electrode materials. The sulfided catalyst can exhibit electrocatalytic performance close to that of noble metal-based catalysts, realizing green and efficient energy production and processing. Therefore, in recent years, sulfided catalysts prepared by POMs have become a research hotspot in green chemistry. This paper reviews the research progress of POMs-based sulfided catalysts in the HDS and HER fields, focusing on the working principles and interrelationships of the two types of processes. The catalytic mechanism, structural advantages and existing problems of POMs-based sulfided catalysts are summarized and discussed. Finally, some prospective of POMs-based sulfided catalysts for their application in those fields are proposed.

Contents

1 Introduction

2 HDS and HER

2.1 HDS

2.2 HER

3 HDS application of MS2with POMs precursors

3.1 HDS catalysts based on Keggin-type POMs

3.2 HDS catalysts based on Anderson-type POMs

3.3 HDS catalysts based on Waugh-type POMs

3.4 HDS catalysts based on Strandberg-type POMs

3.5 HDS catalysts based on new type POMs

4 HER applications of MS2with POMs precursors

4.1 HER catalysts based on MoS2

4.2 HER catalysts based on WS2

5 Conclusion and outlook

Graphical abstract

Keywords

polyoxometalates / hydrodesulfurization / hydrogen evolution reaction / MoS2 / WS2 / green energy / catalytic chemistry

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Changle Yue, Wenjing Bao, Jilei Liang, Yunqi Liu, Daofeng Sun, Yukun Lu. Application of POMs-Based Sulfided Catalyst in Hydrodesulfurization and Hydrogen Evolution by Electrolysis of Water. Progress in Chemistry, 2022, 34(5): 1061-1075 DOI:10.7536/PC210608

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1 Introduction

The extensive use of energy is an important feature of modern civilization, and oil is still the mainstay of current energy. In the current situation, we are facing two major energy problems: environmental pollution caused by petroleum fuels and the development of new energy sources. The development of clean utilization of petroleum fuel and clean alternative energy is an important way to solve the energy crisis. The former is mainly accomplished by reducing the content of sulfur, nitrogen and other elements in petroleum fuels through hydrodesulfurization, while the latter is accomplished by developing new clean energy sources, such as hydrogen energy with high calorific value. Sulfided catalysts based on transition metals are one of the important catalytic materials to solve the above problems because of their unique nano-size and electronic structure, which have excellent performance in catalytic hydrodesulfurization (HDS) and hydrogen evolution from water electrolysis (HER)[1,2].
On the one hand, transition metal-based sulfided catalysts are important and promising HDS materials. Since the 1940s, sulfurized catalysts based on transition metals have been widely studied and applied in the field of HDS catalysts, which has solved the problems of low economic benefits and easy sulfur poisoning of precious metal catalysts, and has become one of the main efficient HDS catalysts[3,4]. Pecoraro and Chianelli first reported that transition metals in the fourth, fifth, and sixth periods may be good HDS catalysts, providing a rationale for the application of transition metals in HDS processes[5]. For example, Mo compounds are ideal materials for the preparation of MoS2-based HDS catalysts with excellent performance and high stability, and have the economic characteristics of high abundance and low price. On the other hand, sulfurized catalysts based on transition metals are also excellent and potential materials for HER. Hydrogen energy has a combustion calorific value three times higher than that of gasoline. Hydrogen production by water electrolysis solves the application problems of high cost, low abundance, slow electrolysis kinetics and high power consumption caused by precious metal-based HER catalysts, and is one of the most ideal hydrogen production methods[6⇓~8]. Before 2005, the performance of sulfided transition metal catalysts, which are mostly used in HDS process, has not been discovered in HER process. After Hinnemann et al. Reported that MoS2 nanoparticles have HER catalytic activity, transition metal sulfides (such as MoS2 and WS2) have attracted more and more attention and become one of the important active phases of efficient sulfided HER catalysts[9]. In conclusion, transition metal-based sulfided catalysts play a key role in two current energy issues. Among them, MoS2 and WS2 are the two most widely studied and used transition metal sulfided catalysts. MoS2 is not only used as a high performance HDS catalyst to reduce the sulfur content in petroleum, but also shines brilliantly in the efficient and green hydrogen production process. This is due to the high valence, unique crystal structure and thermal stability of transition metal sulfide-based materials. The high valence state of transition metals is conducive to the realization of electron transfer with doped elements, the unique and rich crystal structure is conducive to the optimization of atomic control of precursors, and the excellent thermal stability improves the feasibility of catalysts in practical applications, so these materials have become potential electrochemical catalytic materials[10].
Monolayer MoS2 and WS2 are a class of band-gap two-dimensional semiconductors with high in-plane carrier mobility. As one of the representatives of non-noble metal sulfurized HER catalysts, the poor catalytic efficiency of its inert basal plane leads to the slow improvement of HER performance. In recent years, nanosheets, nanofilms and nanotubes with different morphologies have emerged to solve this problem[12][13⇓⇓⇓⇓~18][19][20]. As typical examples of two-dimensional transition metal disulfides (TMDs), the structures of MoS2 and WS2 are composed of S-Mo (W) -S trilayers, which are connected by van der Waals forces. The truncated triangular structure of the monolayer exposes Mo/W edges and S edges, and when supported on Au (111), high-order pyrolytic graphite or graphitic carbon, the Mo/W edges are mainly exposed[21,22][23][23,24][25][26]. As shown in the atomic sphere model of Co/Ni-doped MoS2 in Fig. 1, the Mo edge without S coverage is unstable, so S atoms are adsorbed on the ($10\bar{1}0$) edge, forming a partially (50%) or fully (100%) covered Mo edge. As shown in Fig. 2, high-angle annular dark-field scanning transmission electron microscopy was able to determine the number of S-Mo-S layers, MoS2 and Co-doped MoS2 clusters were observed[27]. Grønborg et al confirmed by this method that Co or Ni doping makes the cluster morphology close to hexagon, exposes more S-edges and significantly improves the catalytic performance of MoS2, which is consistent with STM and DFT studies[27⇓~29]. According to the stacking sequence of the MoS2 and WS2 layers, they are divided into metallic metastable 3 R () phase, 1 T (octahedral Oh), and semiconducting stable 2 H (triangular pyramidal D3h) phases, whose interconversion involves a lateral shift of the S plane[30⇓⇓~33]. Because of this instability of the octahedral 1 T phase, it has not been found in nature. Independent layers of the 1 T phase polymorph can be achieved by solvation and reduction of intercalated alkali metals (Li, etc.), transition metals (Re, etc.), but are thermodynamically unfavorable, gradually transforming into the 2 H phase at room temperature[34,35].
As a well-defined inorganic nanocluster composed of a variety of transition metals and oxygen atoms, Polyoxometalates (POMs) are suitable precursors for the preparation of such emerging transition metal sulfided electrode materials MoS2, WS2, enabling the green and efficient preparation of sulfided transition metal catalysts. This is mainly attributed to the composition and structural advantages of POMs: 1) nano-scale size and high structural stability; 2) that electron gain and loss can be realize quickly and reversibly, and the electronic structure is easy to regulate and control; 3) The structure is clear, such as Anderson, Keggin and other structural types, which can realize multi-metal doping at the single molecule level; 4) The spatial structure is uniform and adjustable, and high-performance HER and HDS catalysts can be derived respectively by regulating the assembly, which is beneficial to defining the reaction active phase and the reaction active mechanism[36]. The preparation of novel structural nanomaterials using crystalline complexes as precursors is one of the hot research fields recently, but there are few reports on the use of POMs as precursors.This special material has many advantages in structure and composition. After screening and optimization, it can show the electrocatalytic performance close to that of precious metal-based catalysts, and realize the green and efficient preparation and treatment of energy[37]. In this paper, the research progress of sulfurized catalysts based on POMs in HDS and HER processes is reviewed, and the catalytic mechanism, assembly rules and the latest progress of sulfurized catalysts based on POMs in HDS and HER processes are summarized and discussed. The advantages and disadvantages of these catalysts in the two fields are analyzed, and their application prospects are prospected.

2 HD S and HER

With the continuous improvement of oil quality requirements, high activity desulfurization catalysts have become a hot research topic. Sulfided catalysts were initially widely used as HDS catalysts because of their superior HDS performance and low production cost. The focus of research is to improve the number of active sites in the active phase of the catalyst and the catalytic stability. With more and more attention paid to hydrogen energy, researchers first thought of using non-precious metal catalysts in HER process. Because HER and HDS processes require the reactive phase to have similar ability to adsorb and desorb hydrogen atoms, sulfurized catalysts based on POMs have gradually shown excellent performance comparable to noble metal catalysts in the field of electrolytic water HER. From the point of view of reaction process, HDS and HER have different reaction processes. In HDS, organic molecules need to be adsorbed and activated by the catalyst, react with hydrogen and decompose to produce H2S or sulfur-containing hydrocarbons and separate them, so as to achieve the effect of desulfurization. In HER, hydrogen ions are converted into hydrogen gas and released by electrolysis of water, mainly through chemical reaction coupled with electron transfer on the electrode. From the perspective of intermediates, the intermediates of HDS and HER adsorb hydrogen atoms on the active sites of the catalyst surface, so the binding ability of hydrogen on the catalyst surface in these two processes has similar requirements. Therefore, researchers have now found that the catalyst metal volcano diagram applied to HDS is also a function of Δ G H *[38,39]. From the composition of the active phase, it has been proved that bimetallic sulfided catalysts have more edge active sites, higher catalytic performance and stability than monometallic catalysts, and POMs are high-quality platforms for bimetallic explicit structural assembly and adjustment. From the reaction mechanism point of view, it has been proved that the Mo/W edge and Co/Ni-doped S edge of sulfided catalysts are the main reaction sites of HDS and HER, which have Δ G H * values closer to 0 than the basal plane, promoting the dissociation of H2 and the adsorption and desorption of H. Ideal HDS and HER catalysts need to expose a large number of active sites, which requires smaller size and higher dispersion. This is the key to the preparation strategy of both catalysts[40,41]. Although a catalyst with excellent HDS performance does not necessarily have good HER performance, a good HDS catalyst is a reasonable choice for the preliminary screening of HER catalysts, and vice versa, both of them have their merits.

2.1 HDS

Affected by the increasing difficulty of oil exploitation, how to reduce the sulfur content of oil products and maintain the stability of the cost is a difficult problem faced by today's oil processing[42]. In addition to sulfur-containing oxides mainly containing sulfur dioxide, alkyl sulfides in oil products are also converted into high molecular weight organic aromatic cyclic sulfides, such as dibenzothiophenes, under high temperature and high pressure conditions of processing[43,44]. These sulfides exist in the product oil, affecting the performance of industrial engines, corroding equipment and pipelines, causing catalyst deactivation, and greatly increasing the difficulty and cost of petroleum processing[45]. Therefore, the desulfurization of oil products is very important, and one of the least cost-effective ways to solve this problem is to develop HDS catalysts with high activity[46].
HDS is the most widely used and efficient oil desulfurization technology, which is carried out by catalytic hydrogenation at a certain temperature and pressure to remove sulfur atoms in petroleum fractions in the form of H2S gases or sulfur-containing hydrocarbons, as well as nitrogen, oxygen and other heteroatoms and metal elements[47]. The process involves carbon-sulfur bond cleavage, releasing H2S gas and sulfur-free hydrocarbons, and can be divided into direct and indirect mechanisms[48]. The direct mechanism, also known as hydrogenolysis pathway, can destroy the C-S bond by hydrogenolysis or direct desulfurization, replacing the S atom in the C-S bond with hydrogen, and the consumption of hydrogen is small. The indirect mechanism, also known as the hydrogenation pathway, requires increasing the saturation of the sulfur-containing aromatic ring prior to removal of the S atom. The choice of the two pathways is influenced by factors such as molecular structure and catalyst type. Aliphatic sulfur compounds (e.g., thiols and sulfides) undergo HDS reaction via hydrogenolysis pathway, which is attributed to the high electron density of S atom and weak C — S bond. Aromatic sulfur (such as 4,6-DMDBT) is affected by steric hindrance and needs to saturate the aromatic ring and weaken the C — S bond[49]. From the catalyst point of view, CoMo-based catalysts prefer the direct route, while NiMo and NiW-based catalysts mainly use the hydrogenation route for HDS. The HDS activity of CoMo is higher than that of NiMo and NiW, especially when hydrogen supply is limited[50]. The process has high desulfurization speed but high cost, and it is difficult to effectively remove the complex 4,6-DMDBT. Taking benzothiophene as an example, its HDS process is shown in Scheme 1. HDS catalysts, represented by sulfided catalysts, have emerged as the times require and have been continuously improved, showing more efficient and excellent sulfide removal and lower assembly and synthesis costs.

2.2 HER

Electrolyzed water includes oxygen evolution reaction OER and hydrogen evolution reaction HER, and the reaction equation is:
H 2 O → H 2 + 1 2 O 2
Among them, the HER reaction occurs at the cathode, two hydrogen ions get two electrons to form hydrogen, and the reaction equation is:
2 ( H + ) + 2 e - → H 2
In 2002, Conway et al. Reported that under acidic conditions, the HER reaction involving catalysts is divided into three steps:[51]
H + + e - → H a d s
H a d s + H + + e - → H 2
H a d s + H a d s → H 2
Among them, step (3) is the Volmer process, that is, electrons combine with H+ on the surface of HER catalyst to form adsorbed hydrogen atoms (Hads), step (4) is the Heyrovsky process, which shows that adsorbed hydrogen atoms react with another electron e- and H+ to release hydrogen, and step (5) is the Tafel process, which refers to the reaction of two adsorbed hydrogen atoms combining to form hydrogen and releasing. An overpotential well above the thermodynamic minimum of 1.23 V is required in practice, corresponding to a reversible electrolyzer voltage of Δ E r e v 0 , 298 = 1.23 V and a thermoneutral (heat is not lost or needed) cell voltage of Δ E t h 0 , 298 = 1.48 V under standard temperature and pressure (STP) conditions[52,53]. Exchange current density is another important kinetic parameter in the HER process, and its magnitude affects the electrochemical reaction rate at other potentials[54]. Linear sweep voltammetry (LSV) is a commonly used electrochemical test method, which can reflect the hydrogen evolution performance of catalysts by electrolysis of water according to the curve relationship between response current density and potential, and obtain the thermodynamic and kinetic parameters of materials. In addition, the Tafel slope is also an important feature to judge the rate-determining step of the HER reaction, which can be further transformed and calculated by the LSV curve. In general, the Tafel slope and the exchange current density can be used to predict the kinetic process of the HER reaction. The Tafel equation can be used to describe the current-potential relationship at a significant overpotential (η):
η = b l o g ( j / j 0 )
Where J is the current density, j0 is the AC current density, and B is the Tafel slope.
The ideal catalyst has low overpotential, low Tafel slope and high exchange current density, and the catalyst with high exchange current density at the same overpotential has better catalytic performance. The HER process at the active site of the catalyst can also be divided into three parts: hydrogen ion adsorption, hydrogen generation, and hydrogen desorption. If the adsorption capacity of H on the catalyst surface is too strong, it is difficult for hydrogen to desorb, and if it is too weak, the hydrogen evolution process is difficult to carry out, and the HER performance is the best when the adsorption competition reaches equilibrium[55,56]. The Gibbs free energy of adsorbed hydrogen (Δ G H *) is of great significance to identify the exchange current density of different metal-based materials[57⇓~59]. The Δ G H * is plotted against the exchange current density, and the curve is volcano-shaped (Fig. 3). Pt group metals are located at the peak of the volcano, and the Δ G H * near zero means the highest HER activity[24]. The volcano diagram is an example of Sabatier's rule, which States that the intermediate compound between the catalyst surface and the reactant must be both stable enough to form a sufficient amount of intermediate product and unstable enough to decompose to produce the final product. The metal on the left side of Pt binds more strongly to H and hinders H2 release; The metal on the right side of Pt is more weakly bound to H and cannot stabilize the intermediate state, which coincides with the previous discussion on adsorption and desorption[58]. Quantum chemical calculations show that Δ G H * is not only a powerful tool to describe the properties of pure metal-based HER materials, but also applicable to transition metal compounds, alloys, and enzymes[9,57]. For example, Jaramillo et al. Synthesized MoS2 nanoparticles on Au (111) under ultra-high pressure, which proved that the active sites of MoS2 nanoparticles were indeed edges, and found that the volcano relationship between HER exchange current density and DFT calculated value of Δ G H * proposed by Nørskov et al[24].

3 HDS application of MS2 with POMs as precursor

For more than a century, the active phase metals of sulfided HDS catalysts are mainly Mo/W and Ni/Co, which are usually supported on inexpensive and highly mesoporous supports, such as Al2O3 or SiO2, by impregnation[60][61]. The incorporation of heteroatoms (Ga, Ca, etc.) can change the strong metal-support interaction between the support and the metal component and improve its HDS performance[56,62,63]. The active metal precursor can come from different metal salts or from composite metal salts, and the active phase of the catalyst prepared by using the composite metal salts as the precursor has higher dispersibility. At present, the sulfided HDS catalyst is mainly prepared by oxidation sulfidation method, and the MoS2 catalyst containing Ni/Co promoter is supported on Al2O3 and other carriers for further sulfidation[64]. One of the ways to improve the activity of HDS catalysts is to make Mo closely combined with Ni/Co promoter atoms. van Veen et al. Have proposed that the degree of close contact between Ni/Co promoter and Mo atoms can be used as a standard to measure the role of promoters[65]. Therefore, the new preparation method of POMs containing both Mo and Ni/Co as the active phase precursor has become a hot spot[66]. It is worth noting that Ni (Co) -Mo-based POMs can achieve efficient polymerization of multimetals through the controllable assembly of different metals at the molecular level, and many researchers have devoted themselves to the design of catalytic materials with excellent HDS activity by using POMs precursors with different structural types.

3.1 HDS catalyst based on Keggin POMs

Keggin-type POMs are currently one of the most widely used precursors for the synthesis of HDS catalysts, and their structures are shown in Fig. 4[67]. Griboval et al. First proved that the activity of HDS catalyst prepared with Keggin-type POMs as precursor was significantly higher than that of conventional catalyst, because Keggin-type phosphomolybdic acid clusters improved the dispersion of active components[68]. The Keggin-type POMs precursor-prepared catalyst exhibited higher activity in HDS than the conventional Mo/W-based catalyst, which was attributed to the better interaction between the oxymolybdenum phase and the promoter[69]. Nikulshin et al., using nickel citrate and Keggin-type phosphomolybdic acid to prepare a Ni-CA-PW/Al2O3 catalyst supported on a γ-Al2O3 with high catalytic activity, demonstrated that the Ni/W ratio had a significant effect on the composition and morphological characteristics of the NiWS active phase and its catalytic performance[70]. They also prepared MoWS bulk catalyst by acid etching method, which confirmed that MoWS mixed active phase existed and had higher HDS performance than single metal[71]. Similarly, by studying the active phase of NiWS, Guevara-Lara et al. demonstrated that the doping position of Ni in tungstate and the pH value of the impregnation solution used for dispersion have different effects on the degree of sulfidation and the catalytic activity of NiWS (Fig. 5)[72]. The special trimetallic NiMon W 12 - n S catalyst shows that the presence of Ni does not hinder the formation of mixed clusters in the POMs based catalyst, proving that the intermetallic synergism brings efficient HDS performance[73]. In addition, Cu2+ can also be doped with Keggin-type POMs to prepare HDS catalysts[74].
The high HDS activity of HDS catalysts based on Keggin-type POMs as precursors is mainly due to the high dispersion of the active component. From the microscopic point of view, the molecular size of Keggin-type POMs is about 1. 3 nm, which is easy to be vulcanized and form a shorter MoS2/WS2 lamellar structure and less stacking layers, with better dispersion. In addition, the atomic ratio of Ni (Co)/Mo (W) in Keggin POMs is relatively small, so increasing the atomic ratio is a good way to improve the activity of HDS catalysts.

3.2 HDS catalyst based on Anderson structure POMs

Anderson structure POMs have a special D3h symmetry structure, and the promoter atoms Co/Ni are wrapped by Mo/W atoms, which is easier to form an active phase after sulfidation. Recent studies have demonstrated the role of heteroatoms in the formation of HDS active sites and catalysis, and POMs are effective precursors for the multilayer active phase of hydrofining catalysts. Among them, the heteroatoms promote the electron density optimization of Mo antibonding in the active mixed sulfide phase, thus promoting the generation of active centers in the HDS reaction, and the doping of different types of heteroatoms plays a key role in the improvement of the intrinsic activity of the catalyst[75].
In 1990, van Veen et al. Directly confirmed that HDS catalysts prepared by Anderson POMs as precursors had good catalytic potential, and reported that the close contact between the main catalyst metal and the promoter metal could improve its catalytic efficiency[65]. Taking Co as an example, previous work has demonstrated that increasing the precursor Co/ (Co + Mo) ratio can improve the hydrogenation performance of the catalyst, which coincides with the study of Keggin-type POMs as the active phase precursor (Fig. 6)[76]. Recent studies have shown that FeMo, CoMo and NiMo supported on β zeolite prepared by Anderson POMs have high conversion of thiophene, and CoMo and NiMo materials have more highly active sites[44]. In addition to the doping of promoters, surface modification is also one of the effective strategies to improve the catalytic performance. Recent studies have shown that sulfur surface-modified NiMo(W)/Al2O3 catalysts have efficient catalytic performance in HDS process[77].
It is common to improve the activity of the catalyst by improving the main catalyst and adding additives by synergistic effect. In addition, the modification of the support is also an effective way to significantly improve the HDS activity of the catalyst. Nikulshin et al. Used carbon-coated alumina as a carrier to support Anderson-type POMs precursors to prepare HDS catalysts, and proved that the carbon content of the carrier could change the packing number/linear size ratio of the active phase particles, thereby controlling the activity and even the selectivity[78].

3.3 HDS catalyst based on POMs with Waugh structure

In Ni-Mo POMs with Waugh structure, Ni and Mo atoms are located in the same anion cluster. Different from Anderson type, three groups of Mo3O13 are connected by pairwise edge-sharing, which has high stability.
The HDS catalyst prepared by our research group with Waugh-type nickel-molybdenum POMs as the active phase precursor has high dispersion, and the atomic ratio can reach 0.44 by replacing N H 4 + with Ni2+,Ni/Mo by ion exchange method, which is very close to the optimal Ni/Mo atomic ratio of 0.5 (Fig. 7). This Ni/Mo atomic ratio is not only beneficial to the full play of the promoter, but also can reduce the particle size of Mo component to achieve high dispersion of active component[79]. The results show that the greatest advantage of Waugh-type POMs is the high dispersion after calcination, the nickel and molybdenum components will not agglomerate after calcination, and the number of active sites produced is more. However, in the calcination process of conventional catalysts, nickel nitrate and ammonium molybdate produce many large MoO3 particles on the surface of the carrier, which are easy to agglomerate and sulfide into relatively large MoS2 clusters, resulting in a small number of active sites and poor dispersion. Therefore, this characteristic of Waugh-type POMs can make up for the problem that Anderson and Keggin POMs are easy to decompose at high temperature and have few active sites.

3.4 HDS catalyst based on POMs with Strandberg structure

[P2Mo5O23]6- is one of the common POMs with Strandberg structure, and its P/Mo ratio is 2/5. The addition of Co or Ni metal salts to [P2Mo5O23]6- solution can prepare bimetallic catalysts with high activity[73]. Strandberg-type phosphorus-molybdenum-nickel POMs is also one of the precursors for preparing efficient HDS catalysts, which contains promoter P atoms, and the Ni/Mo ratio after ion exchange can be as high as 0.4, which is close to the optimal Ni/Mo ratio of 0.5 for HDS catalysts[80]. After calcination, the catalyst has a well-dispersed multicomponent molybdate phase, and the catalytic effect is excellent.
On the basis of the study of Waugh-type POMs, Liang Jilei et al. Used Strandberg-type P-Mo-Ni POMs as a precursor to prepare a highly efficient HDS catalyst with good dispersion, controllable size, appropriate stacking and easy sulfidation[81]. Strandberg-type POMs can not only greatly promote the formation of highly dispersed Ni-Mo component, but also form abundant NiMoS active sites at lower sulfidation temperature, which greatly improves the catalytic performance. The working principle of this catalyst is shown in Figure 8. This preparation method of POMs provides a deeper understanding of the structure and performance of HDS catalysts, and provides ideas for the rational design and controlled preparation of efficient HDS catalysts.

3.5 HDS catalyst based on novel POMs

With the help of coordination of organic ligands and weak supramolecular interactions, our research group induced the impregnation solution to self-assemble and crystallize into POMs precursors with specific structures, and analyzed the structural guiding effect and the transformation mechanism of the active phase of NiMoS heterostructures by "in situ means" (in situ infrared, XRD, Raman, near-in situ XPS, etc.)[82]. Compared with other HDS catalyst precursors, the novel POMs(Mo2Ni and PMo11Ni) are characterized by the formation of Mo-O-Ni coordination bonds in the anion cluster, and the Ni and Mo atoms can be uniformly dispersed in the single crystal POMs to avoid the aggregation of the active phase of the catalyst. This study not only opens up a new way to understand the composition of the impregnation solution and the formation mechanism of the active phase of the catalyst, but also has important guiding significance for the rational design and preparation of high-performance catalysts.

4 HER application of MS2 with POMs as precursor

At present, in order to realize the development and utilization of sustainable clean energy, researchers are committed to preparing non-precious metal-based HER catalysts for efficient water electrolysis to reduce the cost of water electrolysis based on the characteristics of high energy storage, high abundance and cleanness of hydrogen source. Before 2005, MoS2 was only widely studied as HDS catalyst, solid lubricant, until Hinnemann et al. Reported that MoS2 nanoparticles are active HER catalysts, HER catalysts prepared from MoS2 and related metal sulfides (such as WS2) have attracted researchers' interest in development and use, and the edge sites of MoS2 with high HDS activity (Mo atoms with sulfur vacancies) become active sites for HER[83][84][9][54,85,86]. In addition, Šarić et al. Found that both HER and HDS reactions use hydrogen as the active intermediate by DFT calculation[87]. The classical 2H phase MoS2 edge sites and corner sites are effective for HDS and HER, while the basal plane is inert[88]. The catalytic materials prepared by Mo and W sulfide precursors have tunable stoichiometry, structure and morphology, however, the monometallic MoS2 and WS2 have less exposed active sites, low intrinsic conductivity, low activity and poor stability under alkaline conditions, and their HER activity is far from that of Pt-based catalysts[89]. At present, it mainly aims at two main principles of increasing the number of active sites and improving the conductivity of each active site, and achieves the optimization effect through four methods of increasing the surface area of the material, increasing the active sites, enhancing the conductivity of the catalytic phase or support material, and enhancing the catalytic ability of the active site[90⇓⇓~93]. Among them, the most effective strategy to optimize the morphology and electronic structure of MoS2(WS2) materials is to hybridize the materials by introducing secondary transition metals (such as Co/Ni) to form bimetallic sulfide complexes based on MoS2(WS2))[94⇓⇓~97]. At present, the synergistic effect of bimetals greatly improves the HER performance of single metal, in which Mo and W are common active components, Ni and Co are additives, and ordered crystalline materials based on POMs will be an excellent "pre-assembly platform" to guide the formation of bimetallic sources in a fixed proportion at the molecular level. On the one hand, POMs can provide a variety of early transition metals (TMs) (especially MoVI and WVI)[98⇓⇓⇓~102]; On the other hand, the multiple tunable structures of POMs are beneficial to the introduction of secondary transition metals, and can effectively composite with other materials (such as carbon materials, metal nanomaterials, semiconductor materials, etc.) To enhance the performance of products and form MoS2(WS2) composite systems[103,104]. The d orbitals of both Co and Ni possess more abundant electrons than Mo/W, showing a lower energy barrier (ΔGH*<0) for H adsorption[91]. Therefore, the Mo (W)/Co (Ni) bimetallic sulfide composites all have excellent HER performance, which has been demonstrated in both theoretical and experimental works[89,94].

4.1 MoS2 based HER catalyst

The existing computational and experimental studies have shown that MoS2 are promising and versatile sulfidation catalytic materials, such as energy storage and conversion and sensing[9,105,106][8,107]. The MoS2 has a graphene-like structure, a large specific surface area and a ΔGH* close to that of Pt, and its catalytic activity has a direct structure-activity relationship with the edge length[108~111][112]. Some new bimetallic sulfide materials with excellent electrochemical properties have been prepared by various methods, such as immersion synthesis, exfoliation, chemical vapor deposition, and electrochemical deposition[26,110][113,114][115,116].
Impregnation synthesis is the most commonly used method to prepare MoS2 nanomaterials using POMs. The atomic-scale structure and morphology of materials are affected by reaction parameters, such as annealing temperature, sulfidation atmosphere, and metal (e.g., Ni/Co) doping. Chorkendorff et al. Used ammonium molybdate as molybdenum source, carbon paper or carbon powder as support material, and Ni salt solution as impregnation doping additive to obtain MoS2 materials by calcination in 10%H2S atmosphere[24]. Impregnation synthesis can be divided into one-pot hydrothermal synthesis and multi-step synthesis. Multi-step synthesis can prepare special morphologies of metal sulfides and MoS2 composites, such as nanospheres and nanosheets, which can significantly improve HER, OER and even OWS properties, but the experimental conditions are harsh and the energy cost is high, so the mechanism study is difficult[95⇓~97].
The one-pot hydrothermal synthesis method has been widely used for the synthesis of POMs-based Mo sulfides due to the advantages of low cost, high yield, and simple procedure. This hydrothermal synthesis method is easier to obtain the intermediate state, metastable state and other special structures (such as 1T-MoS2 phase structure) of the product, and the product has the characteristics of high dispersion, good crystallinity, and easy control of morphology. In 2015, Song Li et al. Used ammonium molybdate and thiourea to synthesize 2H-MoS2 and 1T-MoS2, indicating that the intercalation of NH 4 + into molybdenum disulfide interlayer was the main factor for the formation of 1T-MoS2 phase[117]. In the two different MoS2 phases, compared with the stable 2H-MoS2, the metastable 1T-MoS2 has more excellent electron transport ability and HER performance[32,118]. Because of the metastable state, the 1T-MoS2 is easy to transform into stable 2H phase MoS2 in the reaction process, so improving the stability of 1T-MoS2 has become a new development idea. In addition, 1T-MoS2 catalysts with high stability and high HER catalytic performance can also be prepared by organic sulfur sources, which has practical application significance. In 2016, Liu Yingju et al. Used ammonium molybdate and thiourea as molybdenum and sulfur sources, respectively, to prepare edge-rich planar MoS2 nanosheets, proving that the rich edges provide more active sites[119].
Ammonium molybdate, as a commonly used POMs-type molybdenum source, has a butterfly shape similar to the β-Anderson structure, nanoscale size (< 1 nm), and good water solubility. The Anderson-type POMs commonly used for synthesis are denoted as [XMo6O24Hx]n-(X=Zn, Cu, Co, Ni, Fe, etc.), and its special advantage for the preparation of MoS2 nanomaterials is to provide a fixed proportion of bimetallic sources[120,121]. As shown in Fig. 9, in 2018, Lan Yagan et al. Synthesized bimetallic sulfides (M-Mo-S/CC, M = Co, Ni, Fe) grown on carbon cloth (CC) with Anderson-type POMs as bimetallic source by one-pot hydrothermal synthesis[120].
Among them, Co-Mo-S/CC and Ni-Mo-S/CC exhibited low onset potentials of 60 mV, 78 mV and low Tafel slopes of 84 mV·dec-1, 90 mV·dec-1, respectively. The excellent electron transport ability and catalytic HER performance of Co-Mo-S/CC benefit from the stable Co-Mo-S heterostructure formed by the hybridization of CoS2 and MoS2. In addition, this study is the first to demonstrate that M-Mo-S/CC has a bimetallic sulfide composition rather than a metal-doped MoS2structure, which is due to the dominant nucleation reaction in the competition between nucleation and doping, so the morphology of the material is studied and predicted by the nucleation rate of different metals. This study has guiding significance for the exploration of the principle of bimetallic sulfide catalysis. Subsequently, Wei Yongge et al. Used Anderson-type POMs as precursors to dope metal active sites onto 1T-MoS2 from the atomic level, and prepared a series of transition metal and oxygen Co-doped 1 T phase MoS2 nanosheets XO@1T-MoS2(X=Ni, Co, Fe), as shown in Fig. 10[122].
Among them, the NiO@1T-MoS2/CFP(CFP= carbon fiber paper) catalyst has a low onset overpotential of nearly 0 mV, a low Tafel slope of 52 mV·dec-1, a high exchange current density of 0.44 mA·cm-2, and a high stability under strong alkaline conditions, which is superior to the most advanced 20% Pt/C catalyst currently in commercial use. The combined experimental and theoretical results of this study show that precise co-doping of Ni and O atoms in ultrathin 1T-MoS2 nanosheets effectively reduces the kinetic energy barrier required for the initial water dissociation step and promotes the intermediate-state hydrogen production process. The results of this study promote the understanding of single-atom catalytic activation sites, and to some extent, promote the process of designing optimal catalytic systems.
In addition to ammonium molybdate, phosphomolybdic acid is one of the commonly used high-quality molybdenum sources for the preparation of MoS2 from POMs. Phosphomolybdic acid is a Keggin-type POMs anion with a diameter of less than 1 nm, which has good water solubility and strong reversible oxidation. Due to the electrostatic repulsion, phosphomolybdic acid particles can be uniformly dispersed between the layers of graphene oxide solution, so phosphomolybdic acid and graphene oxide are often combined to achieve ideal performance[123]. As shown in Fig. 11, Lan Yagan et al. First used phosphomolybdic acid, thiourea and graphene oxide as precursors to synthesize the MoS2 based nanocomposite MoS2/N-RGO at different hydrothermal temperatures, which has an onset potential as low as 5 mV, a Tafel slope as low as 41.3 mV·dec-1, an exchange current density as high as 7.4×10-4A·cm-2, and ultra-high stability[124]. Density functional theory calculations show that the MoS2-9.5Å has the best catalytic performance among the MoS2 nanosheets with the interlayer spacing ranging from 6.2 to 9.55 Å, which is attributed to the more efficient electron transfer and hydrogen production rate due to the larger interlayer spacing.
Soon after, Singh et al. Used a one-pot hydrothermal synthesis method combining phosphomolybdic acid and graphene oxide to synthesize MoSx-rGO composite nanomaterials with H2S as the sulfur source[125]. The material, composed of MoS3 particles and a small amount of MoS2 nanosheets, exhibited excellent HER catalytic activity with low onset overpotential and high current density. Among them, the Tafel slope of the MoS2-rGO nanocomposite is 41.7 mV·dec-1, indicating that the HER catalyzed by MoS2 follows the Volmer-Heyrovsky mechanism, and the electrochemical desorption of hydrogen is the rate-limiting step. This study also provides a theoretical basis for the subsequent improvement of material properties. In 2019, Zhang Bangwen et al. Used phosphomolybdic acid as the molybdenum source, graphene oxide as the carrier, and L-cysteine as the reducing dopant to obtain the UT-MoS/rGO composite by one-pot hydrothermal synthesis, which has an initial overpotential of − 66 mV and a Tafel slope of 42.9 mV·dec-1 in the HER reaction, and has excellent HER catalytic performance and high stability[126].
In addition to graphene oxide, carbon cloth and carbon nanotubes are commonly used to synthesize MoS2 catalysts with POMs, which are attributed to the high specific surface area, abundant pore structure and good conductivity of carbon materials. Recently, Lu Yukun et al. Used a special Evans-Showell type CoMo-based POM precisely adjusted at the atomic level as the precursor to prepare a CoMoS/CC with high full water decomposition performance, and the overpotential was only 36 mV under strong alkaline conditions with a current density of 10 mA·cm-2 (Fig. 12)[127]. Taking advantage of the low cost, high conductivity, high physical strength and good flexibility of carbon cloth, this study proves that the heterostructure provides abundant defects and active sites at the heterointerface, and realizes the ultra-high water electrolysis performance of catalytic materials. Similarly, Sun Licheng et al. Used Anderson-type POMs as precursors to prepare vertically aligned O-CoMoS sheets on flexible carbon fiber cloth as bifunctional electrocatalysts, demonstrating again the unique advantages and efficient HER performance of POMs as bimetallic precursors (Fig. 13)[128]. In addition to carbon materials, the composite of POMs and organic materials has also become one of the feasible methods to prepare high-performance HER catalysts. In 2019, Qiu Yunfeng et al. Used polypyrrole salt precursor of phosphomolybdic acid as molybdenum source and elemental sulfur as sulfur source to prepare mesoporous hollow MoS2/C800 nanospheres by annealing at 800 ° C[129]. The material has many lattice defects and large exposure of active sites, with an overpotential of 207 mV and a Tafel slope of 73 mV·dec-1 at a current density of 10 mA·cm-2. Recently, Pang et al. Synthesized highly dispersed CoS2-MoS2 and Ni3S2-MoS2 bimetallic sulfides with mesoporous structure from Mo-based POMs based metal-organic polymers by one-pot hydrothermal synthesis[130]. The overpotentials of these two sulfide 1:1 composites at 10 mA·cm-2 are 222 and 224 mV, respectively, and the Tafel slopes in 0.5 mol/L H2SO4 are 64.2 and 65.7 mV·dec-1, respectively, outperforming most of the MoS2-based non-noble metal electrocatalysts prepared from POMs. In addition, POMs are often combined with metal-organic frameworks to prepare nano-HER materials, but there are few reports on the MoS2 prepared by this method[100].

4.2 WS2 based HER catalyst

The study shows that from the nanocrystal point of view, Ni/Co-doped WS2 materials have higher electrocatalytic HER performance compared with WS2, which is due to the synergistic effect of Ni/Co atoms and WS2, which shows a larger truncation of the hexagonal-like morphology in the nanocrystal and exposes more S-edge active sites[25]. From a thermodynamic point of view, Co only incorporates itself into the S-edge, so the H-atom Gibbs adsorption free energy (Δ G H *) value of the W-edge is not affected. But, at the S-edge, the Δ G H * value of Co-W-S synthesized by the Co-impregnation method is 0.07 eV, which is 0.15 eV lower than that of undoped WS2, and Co creates new sites that are more active than before doping[36]. In other words, the presence of Co makes the S edge, which is usually less active, acquire higher activity, increasing the number of active sites of the material. Therefore, Co/Ni doping is often used to prepare bimetallic sulfides with WS2 to continuously improve the HER performance of the materials. In 2009, Chorkendorff et al. Reported that ammonium tungstate was loaded on carbon paper by high temperature calcination method to prepare WS2 and Co-W-S, and the Tafel slope of Co-W-S material was 132 mV·dec-1[36]. The results show that WS2 is irreversibly oxidized at high anodic potential and has almost the same activity as MoS2. The catalytic activity of different materials was calculated to be WS2<MoS2=Co-Mo-S<Co-W-S by DFT, which provided a theoretical basis for the subsequent exploration of WS2 materials. In addition, Se atoms are able to dope in W sulfides, providing more defect sites with lower Δ G H * values as HER active sites (Fig. 14).
In addition to heteroatom doping, multi-system WS2 composite is another effective method to break through the bottleneck of single HER performance. As a semiconductor material, TiO2 has the advantages of high activity, mild reaction conditions and low preparation cost. Through the dual-system composite of TiO2 and WS2, not only the dispersion of WS2 active sites was realized, but also the conductivity of TiO2 was improved, which realized the green and low-cost preparation of non-noble metal-based HER electrocatalysis. Liu Shanhu et al. Used TiO2 nanobelts as a substrate to synthesize WS2@TiO2 composites by a simple hydrothermal method[131]. The material is composed of strip-shaped TiO2 and sheet-shaped WS2 coated on the outer layer, and has better synergistic effect. Through three-electrode electrolytic water HER test, the overpotential of the catalyst is 150 mV and the Tafel slope is 120 mV·dec-1 under alkaline conditions at a current density of 10 mA·cm-1, which is much higher than the excellent catalytic performance and stability of single WS2 and TiO2 systems, and has a good application prospect.
However, because there are few reports on POMs-based WS2 electrocatalysts, the reported POMs-based WS2 catalysts have low activity density as a whole, and have the problems of poor electrical transport or low electrical efficiency, which are still far from satisfactory compared with Pt and need more exploration and improvement. However, this does not mean that the HER catalytic performance of WS2 has not been explored. In the field of photocatalytic HER, WS2 materials have been widely discussed and applied, which have the separation efficiency of high photogenerated carriers and can achieve efficient photocatalytic water splitting for hydrogen production, especially the improvement of 1T-WS2 and 2H-WS2 materials has opened up a new way to regulate the intrinsic HER activity.
From the above discussion, it can be concluded that there are three main ways to improve the performance of HER catalysts: first, high temperature pyrolysis sulfidation can improve the activity, stability and conductivity of HER catalysts based on POMs; The second is to promote the heterostructure of catalytic materials through the synergistic effect of heteroatom (such as Ni, Mo and P) doping and Mo/W sulfidation phase, so as to achieve efficient HER catalysis of bimetals. The third is to complement the advantages of POMs by compounding with other systems, such as the high conductivity of carbon systems or the self-assembly of organic systems, while enhancing the regulation and dispersion of active sites. Although high temperature pyrolysis leads to sintering and aggregation of catalyst particles to a certain extent, high dispersion of catalyst particles can be prepared by doping of heteroatoms and compounding of multiple systems. In addition to enhancing the activity, conductivity, and stability of the catalyst, broadening the pH range for catalyst application is also crucial for the preparation of HER catalysts with practical applications. In general, there are few studies on sulfurized POMs based HER catalysts, especially on WS2, so it is still necessary to explore the potential of different kinds of POMs and their derivatives as catalyst precursors, and to learn from the experience of carbonized and phosphated POMs based catalysts to improve their performance.

5 Conclusion and prospect

Due to the special structure and electron-rich properties of Ni/Co-doped Mo/W-based POMs, the sulfided catalysts using such POMs and their derivatives as precursors show catalytic performance close to that of noble metal-based catalysts, which has great potential in the fields of HDS and HER. The precursor prepared based on POMs has the following four unique advantages: firstly, the problem of close contact between the promoter and the main catalyst is solved from the perspective of raw materials, and the catalytic performance of the active phase is improved; The second is to use the different structures of POMs to realize the controllable structure adjustment of catalysts, which is helpful to prepare porous materials with different application conditions. The third is to realize the high dispersion of the active phase, so that the catalyst has smaller size and higher surface area, especially the Waugh-type POMs has excellent thermal stability, and the prepared catalyst avoids agglomeration and sintering after high temperature calcination; Fourthly, the sulfurized catalyst based on POMs contains sulfur itself, which can reduce and avoid sulfur poisoning of the catalyst.
In the future development of HDS catalysts, the main direction should be to explore how to control the reaction conditions to synthesize POMs precursors with a Ni (Co)/Mo (W) atomic ratio close to 0.5 and excellent pore structure properties. At the same time, it is vulcanized into a single structure hydrogenation active phase with controllable polymerization degree, dispersion and size. Taking this as a model system, it is particularly important to investigate the sulfidation behavior of POMs and the conversion mechanism of its derived CoMoS active phase, to explore the structure-oriented effect and directional control mechanism of the structural characteristics of POMs on the hydrogenation active phase, and to deeply understand and elaborate the structure-activity relationship between the microstructure of the hydrogenation active phase and the catalytic mechanism. The main research direction of sulfurized HER catalysts based on POMs is mainly focused on the preparation of bimetallic sulfides with MoS2 from POMs precursors. The main current problems are the Hush experimental conditions and the high energy costs typically encountered in such preparations. Because dissociative metal salts with discrete composition participate in the reaction, metal ions have different nucleation rates in most cases, and different metal sulfides tend to isolate during growth, thus making the growth process more complex and arduous. Therefore, significant challenges remain to achieve the engineering of highly dispersed bimetallic sulfided catalysts. More heteroatoms that can be incorporated into POMs need to be discovered and studied, which is of great significance for the application of various POMs in HER. At the same time, although encouraging results have been achieved at laboratory scale, only experiments using properly designed equipment can demonstrate the real potential of these catalysts in large-scale applications and make a key step towards the early realization of truly efficient green energy utilization.

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]

Huang L B, Zhao L, Zhang Y, Chen Y Y, Zhang Q H, Luo H, Zhang X, Tang T, Gu L, Hu J S. Adv. Energy Mater., 2018, 8(21): 1800734.
[2]

Huang T T, Peng Q Y, Gai H J, Fan Y. Energy Fuels, 2021, 35(3): 2402.
[3]

Taylor M J, Durndell L J, Isaacs M A, Parlett C M A, Wilson K, Lee A F, Kyriakou G. Appl. Catal. B: Environ., 2016, 180: 580.
[4]

Nogueira A, Znaiguia R, Uzio D, Afanasiev P, Berhault G. Appl. Catal. A: Gen., 2012, 429/430: 92.
[5]

Pecoraro T A, Chianelli R R. J. Catal., 1981, 67(5): 430.
[6]

Zeng K, Zhang D K. Prog. Energy Combust. Sci., 2010, 36(3): 307.
[7]

Rausch B, Symes M D, Chisholm G, Cronin L. Science, 2014, 345(6202): 1326.
[8]

Wang J H, Yan M Y, Zhao K N, Liao X B, Wang P Y, Pan X L, Yang W, Mai L Q. Adv. Mater., 2017, 29(7): 1604464.
[9]

Hinnemann B, Moses P G, Bonde J, Jørgensen K P, Nielsen J H, Horch S, Chorkendorff I, Nørskov J K. J. Am. Chem. Soc., 2005, 127(15): 5308.
[10]

Deng X H, Xu G Y, Zhang Y J, Wang L, Zhang J J, Li J F, Fu X Z, Luo J L. Angew. Chem. Int. Ed., 2021, 60(37): 20535.
[11]

Díaz de LeÓn J, Ramesh Kumar C, Antúnez-García J, Fuentes-Moyado S. Catalysts, 2019, 9(1): 87.
[12]

Sobczynski A, Yildiz A, Bard A J, Campion A, Fox M A, Mallouk T, Webber S E, White J M. J. Phys. Chem., 1988, 92(8): 2311.
[13]

Voiry D, Yamaguchi H, Li J W, Silva R, Alves D C B, Fujita T, Chen M W, Asefa T, Shenoy V B, Eda G, Chhowalla M. Nat. Mater., 2013, 12(9): 850.
[14]

Yang J, Voiry D, Ahn S J, Kang D, Kim A Y, Chhowalla M, Shin H S. Angew. Chem. Int. Ed., 2013, 52(51): 13751.
[15]

Lukowski M A, Daniel A S, English C R, Meng F, Forticaux A, Hamers R J, Jin S. Energy Environ. Sci., 2014, 7(8): 2608.
[16]

Duan J J, Chen S, Chambers B A, Andersson G G, Qiao S Z. Adv. Mater., 2015, 27(28): 4234.
[17]

Ambrosi A, Sofer Z, Pumera M. Chem. Commun., 2015, 51(40): 8450.
[18]

Zhang J, Wang Q, Wang L H, Li X A, Huang W. Nanoscale, 2015, 7(23): 10391.
[19]

Cheng L, Huang W J, Gong Q F, Liu C H, Liu Z, Li Y G, Dai H J. Angew. Chem. Int. Ed., 2014, 53(30): 7860.
[20]

Xu K, Wang F M, Wang Z X, Zhan X Y, Wang Q S, Cheng Z Z, Safdar M, He J. ACS Nano, 2014, 8(8): 8468.
[21]

Zhang X, Lai Z C, Tan C L, Zhang H. Angew. Chem. Int. Ed., 2016, 55(31): 8816.
[22]

Zhang G, Liu H J, Qu J H, Li J H. Energy Environ. Sci., 2016, 9(4): 1190.
[23]

Helveg S, Lauritsen J V, Lægsgaard E, Stensgaard I, Nørskov J K, Clausen B S, Topsøe H, Besenbacher F. Phys. Rev. Lett., 2000, 84(5): 951.
[24]

Jaramillo T F, Jorgensen K P, Bonde J, Nielsen J H, Horch S, Chorkendorff I. Science, 2007, 317(5834): 100.
[25]

Kibsgaard J, Lauritsen J V, Lægsgaard E, Clausen B S, Topsøe H, Besenbacher F. J. Am. Chem. Soc., 2006, 128(42): 13950.
[26]

Brorson M, Carlsson A, Topsøe H. Catal. Today, 2007, 123(1/4): 31.
[27]

Grønborg S S, Salazar N, Bruix A, Rodríguez-Fernández J, Thomsen S D, Hammer B, Lauritsen J V. Nat. Commun., 2018, 9(1): 2211.
[28]

Lauritsen J V, Helveg S, Lægsgaard E, Stensgaard I, Clausen B S, Topsøe H, Besenbacher F. J. Catal., 2001, 197(1): 1.
[29]

Byskov L S, Nørskov J K, Clausen B S, Topsøe H. J. Catal., 1999, 187(1): 109.
[30]

Toh R J, Sofer Z, Luxa J, Sedmidubský D, Pumera M. Chem. Commun., 2017, 53(21): 3054.
[31]

Enyashin A N, Yadgarov L, Houben L, Popov I, Weidenbach M, Tenne R, Bar-Sadan M, Seifert G. J. Phys. Chem. C, 2011, 115(50): 24586.
[32]

Chhowalla M, Shin H S, Eda G, Li L J, Loh K P, Zhang H. Nat. Chem., 2013, 5(4): 263.
[33]

Lin Y C, Dumcenco D O, Huang Y S, Suenaga K. Nat. Nanotechnol., 2014, 9(5): 391.
[34]

Wypych F, Solenthaler C, Prins R, Weber T. J. Solid State Chem., 1999, 144(2): 430.
[35]

Heising J, Kanatzidis M G. J. Am. Chem. Soc., 1999, 121(4): 638.
[36]

Bonde J, Moses P G, Jaramillo T F, Nørskov J K, Chorkendorff I. Faraday Discuss., 2009, 140: 219.
[37]

Horn M R, Singh A, Alomari S, Goberna-FerrÓn S, Benages-Vilau R, Chodankar N, Motta N, Ostrikov K K, MacLeod J, Sonar P, Gomez-Romero P, Dubal D. Energy Environ. Sci., 2021, 14(4): 1652.
[38]

Breysse M, Furimsky E, Kasztelan S, Lacroix M, Perot G. Catal. Rev., 2002, 44(4): 651.
[39]

Chianelli R R, Berhault G, Raybaud P, Kasztelan S, Hafner J, Toulhoat H. Appl. Catal. A: Gen., 2002, 227(1-2): 83.
[40]

Han X B, Tang X Y, Lin Y, Gracia-Espino E, Liu S G, Liang H W, Hu G Z, Zhao X J, Liao H G, Tan Y Z, Wagberg T, Xie S Y, Zheng L S. J. Am. Chem. Soc., 2019, 141(1): 232.
[41]

Carlsson A, Brorson M, Topsøe H. J. Catal., 2004, 227(2): 530.
[42]

Cui T Y, Rajendran A, Fan H X, Feng J, Li W Y. Ind. Eng. Chem. Res., 2021, 60(8): 3295.
[43]

Startsev A N. Catal. Rev., 1995, 37(3): 353.
[44]

Puello polo E, Romero Baños M, Fals J F. Prospectiva, 2017, 16(1): 34.
[45]

Srivastava V C. RSC Adv., 2012, 2(4): 759.
[46]

Li D D. Chinese Journal of Catalysis, 2013, 34(1): 48.
[47]

(李大东. 催化学报, 2013, 34(1): 48.)
[48]

Zhu Q L, Zhao X T, Zhao Z X, Ma H J, Deng Y Q. Molecular Catalysis, 2006, 20(4): 372.
[49]

(朱全力, 赵旭涛, 赵振兴, 马洪江, 邓友全. 分子催化, 2006, 20(4): 372.)
[50]

Bello S S, Wang C, Zhang M J, Gao H, Han Z N, Shi L, Su F B, Xu G W. Energy Fuels, 2021, 35(14): 10998.
[51]

Song C S. Catal. Today, 2003, 86(1/4): 211.
[52]

Ding L H, Zheng Y, Zhang Z S, Ring Z, Chen J W. J. Catal., 2006, 241(2): 435.
[53]

Conway B E, Tilak B V. Electrochimica Acta, 2002, 47(22/23): 3571.
[54]

Lyon Y A, Roberts A A, McMillin D R. J. Chem. Educ., 2015, 92(12): 2130.
[55]

Morales-Guio C G, Stern L A, Hu X L. Chem. Soc. Rev., 2014, 43(18): 6555.
[56]

Yan Y, Xia B Y, Xu Z C, Wang X. ACS Catal., 2014, 4(6): 1693.
[57]

Theerthagiri J, Senthil R A, Senthilkumar B, Reddy Polu A, Madhavan J, Ashokkumar M. J. Solid State Chem., 2017, 252: 43.
[58]

Benck J D, Hellstern T R, Kibsgaard J, Chakthranont P, Jaramillo T F. ACS Catal., 2014, 4(11): 3957.
[59]

Greeley J, Jaramillo T F, Bonde J, Chorkendorff I, Nørskov J K. Nat. Mater., 2006, 5(11): 909.
[60]

Nørskov J K, Bligaard T, Logadottir A, Kitchin J R, Chen J G, Pandelov S, Stimming U. J. Electrochem. Soc., 2005, 152(3): J23.
[61]

Greeley J, Nørskov J K, Kibler L A, El-Aziz A M, Kolb D M. ChemPhysChem, 2006, 7(5): 1032.
[62]

Lai W K, Chen Z, Zhu J P, Yang L F, Zheng J B, Yi X D, Fang W P. Nanoscale, 2016, 8(6): 3823.
[63]

Huirache-Acuña R, Nava R, Peza-Ledesma C, Lara-Romero J, Alonso-Núez G, Pawelec B, Rivera-Muñoz E. Materials, 2013, 6(9): 4139.
[64]

Díaz de LeÓn J N. Appl. Catal. B: Environ., 2016, 181: 524.
[65]

Zhou W W, Zhang Y N, Tao X J, Zhou Y S, Wei Q, Ding S J. Fuel, 2018, 228: 152.
[66]

Alonso-Núñez G, Bocarando J, Huirache-Acuña R, Álvarez-Contreras L, Huang Z D, Bensch W, Berhault G, Cruz J, Zepeda T A, Fuentes S. Appl. Catal. A: Gen., 2012, 419-420: 95.
[67]

van Veen J A R, Hendriks P A J M, Romers E J G M, Andrea R R. J. Phys. Chem., 1990, 94(13): 5275.
[68]

Romero-Galarza A, GutiÉrrez-Alejandre A, Ramírez J. J. Catal., 2011, 280(2): 230.
[69]

Zhang H, Yan R Y, Yang L, Diao Y Y, Wang L, Zhang S J. Ind. Eng. Chem. Res., 2013, 52(12): 4484.
[70]

Griboval A, Blanchard P, Payen E, Fournier M, Dubois J L. Catal. Today, 1998, 45(1/4): 277.
[71]

Alsalme A, Alzaqri N, Alsaleh A, Siddiqui M R H, Alotaibi A, Kozhevnikova E F, Kozhevnikov I V. Appl. Catal. B: Environ., 2016, 182: 102.
[72]

Minaev P P, Nikulshin P A, Kulikova M S, Pimerzin A A, Kogan V M. Appl. Catal. A: Gen., 2015, 505: 456.
[73]

Kokliukhin A, Nikulshina M, Mozhaev A, Lancelot C, Lamonier C, Nuns N, Blanchard P, Bugaev A, Nikulshin P. Catal. Today, 2021, 377: 26.
[74]

LÓpez-Benítez A, Guevara-Lara A, Berhault G. ACS Catal., 2019, 9(8): 6711.
[75]

Kokliukhin A, Nikulshina M, Mozhaev A, Lancelot C, Blanchard P, Briois V, Marinova M, Lamonier C, Nikulshin P. J. Catal., 2021, 403: 141.
[76]

Ma Y Q, Liu X P, Li J P, Wang R, Yu M Q. Chem. Pap., 2017, 71(3): 647.
[77]

Nikulshin P, Mozhaev A, Lancelot C, Blanchard P, Payen E, Lamonier C. Comptes Rendus Chimie, 2016, 19(10): 1276.
[78]

Martin C, Lamonier C, Fournier M, MentrÉ O, HarlÉ V, Guillaume D, Payen E. Inorg. Chem., 2004, 43(15): 4636.
[79]

Puello-Polo E, Diaz Y, Brito J L. Catal. Commun., 2017, 99: 89.
[80]

Nikulshin P A, Salnikov V A, Mozhaev A V, Minaev P P, Kogan V M, Pimerzin A A. J. Catal., 2014, 309: 386.
[81]

Liang J L, Liu Y Q, Zhao J C, Li X H, Lu Y K, Wu M M, Liu C G. Catal. Lett., 2014, 144(10): 1735.
[82]

Blanchard P, Lamonier C, Griboval A, Payen E. Appl. Catal. A: Gen., 2007, 322: 33.
[83]

Liang J L, Wu M M, Wei P H, Zhao J C, Huang H, Li C F, Lu Y K, Liu Y Q, Liu C G. J. Catal., 2018, 358: 155.
[84]

Liang J L, Wu M M, Wang J J, Wei P H, Sun B F, Lu Y K, Sun D F, Liu Y Q, Liu C G. Catal. Sci. Technol., 2018, 8(24): 6330.
[85]

Prins R, de Beer V H J, Somorjai G A. Catal. Rev., 1989, 31(1/2): 1.
[86]

Spalvins T. J. Vac. Sci. Technol. A, 1987, 5(2): 212.
[87]

Kibsgaard J, Chen Z B, Reinecke B N, Jaramillo T F. Nat. Mater., 2012, 11(11): 963.
[88]

Deng J, Li H B, Xiao J P, Tu Y C, Deng D H, Yang H X, Tian H F, Li J Q, Ren P J, Bao X H. Energy Environ. Sci., 2015, 8(5): 1594.
[89]

Šarić M, Moses P G, Rossmeisl J. ChemCatChem, 2016, 8(21): 3334.
[90]

Šarić M, Rossmeisl J, Moses P G. Phys. Chem. Chem. Phys., 2017, 19(3): 2017.
[91]

Chen L X, Chen Z W, Wang Y, Yang C C, Jiang Q. ACS Catal., 2018, 8(9): 8107.
[92]

Liu Z X, Yuan X M, Yang P. J. Magn. Magn. Mater., 2018, 461(1): 1.
[93]

Yu Y F, Nam G H, He Q Y, Wu X J, Zhang K, Yang Z Z, Chen J Z, Ma Q L, Zhao M T, Liu Z Q, Ran F R, Wang X Z, Li H, Huang X, Li B, Xiong Q H, Zhang Q, Liu Z, Gu L, Du Y H, Huang W, Zhang H. Nat. Chem, 2018, 10(6): 638.
[94]

Xie J F, Zhang H, Li S, Wang R X, Sun X, Zhou M, Zhou J F, Lou X W D, Xie Y. Adv. Mater., 2013, 25(40): 5807.
[95]

Guo B J, Yu K, Li H L, Song H L, Zhang Y Y, Lei X, Fu H, Tan Y H, Zhu Z Q. ACS Appl. Mater. Interfaces, 2016, 8(8): 5517.
[96]

Hu J, Huang B L, Zhang C X, Wang Z L, An Y M, Zhou D, Lin H, Leung M K H, Yang S H. Energy Environ. Sci., 2017, 10(2): 593.
[97]

Zhang J, Wang T, Pohl D, Rellinghaus B, Dong R H, Liu S H, Zhuang X D, Feng X L. Angew. Chem. Int. Ed., 2016, 128(23): 6814.
[98]

Guo Y N, Tang J, Qian H Y, Wang Z L, Yamauchi Y. Chem. Mater., 2017, 29(13): 5566.
[99]

Yang Y Q, Zhang K, Lin H L, Li X, Chan H C, Yang L C, Gao Q S. ACS Catal., 2017, 7(4): 2357.
[100]

Guo Y X, Gan L F, Shang C S, Wang E K, Wang J. Adv. Funct. Mater., 2017, 27(5): 1602699.
[101]

Miras H N, Vilà-Nadal L, Cronin L. Chem. Soc. Rev., 2014, 43(16): 5679.
[102]

Du D Y, Qin J S, Li S L, Su Z M, Lan Y Q. Chem. Soc. Rev., 2014, 43(13): 4615.
[103]

Wang S S, Yang G Y. Chem. Rev., 2015, 115(11): 4893.
[104]

Zhao J W, Li Y Z, Chen L J, Yang G Y. Chem. Commun., 2016, 52(24): 4418.
[105]

Jiao L, Seow J Y R, Skinner W S, Wang Z U, Jiang H L. Mater. Today, 2019, 27: 43.
[106]

Svatek S A, Antolin E, Lin D Y, Frisenda R, Reuter C, Molina-Mendoza A J, Muñoz M, Agraït N, Ko T S, de Lara D P, Castellanos-Gomez A. J. Mater. Chem. C, 2017, 5(4): 854.
[107]

Bu C H, Liu Y M, Yu Z H, You S J, Huang N, Liang L L, Zhao X Z. ACS Appl. Mater. Interfaces, 2013, 5(15): 7432.
[108]

Jin H Y, Wang J, Su D F, Wei Z Z, Pang Z F, Wang Y. J. Am. Chem. Soc., 2015, 137(7): 2688.
[109]

Perkins F K, Friedman A L, Cobas E, Campbell P M, Jernigan G G, Jonker B T. Nano Lett., 2013, 13(2): 668.
[110]

Li H, Yin Z Y, He Q Y, Li H, Huang X, Lu G, Fam D W H, Tok A I Y, Zhang Q, Zhang H. Small, 2012, 8(1): 63.
[111]

Li L, Li J X, Liu L L, Wang X R, Guo Y, Zhou Y J. ACS Appl. Energy Mater., 2019, 2(2): 1413.
[112]

Li Y G, Wang H L, Xie L M, Liang Y Y, Hong G S, Dai H J. J. Am. Chem. Soc., 2011, 133(19): 7296.
[113]

Sun T, Wang J, Chi X, Lin Y X, Chen Z X, Ling X, Qiu C T, Xu Y S, Song L, Chen W, Su C L. ACS Catal., 2018, 8(8): 7585.
[114]

Venkateshwaran S, Senthil Kumar S M. ACS Sustainable Chem. Eng., 2019, 7(2): 2008.
[115]

Hu Z J, Bao Y J, Li Z W, Gong Y J, Feng R, Xiao Y D, Wu X C, Zhang Z H, Zhu X, Ajayan P M, Fang Z Y. Sci. Bull., 2017, 62(1): 16.
[116]

Liu K K, Zhang W J, Lee Y H, Lin Y C, Chang M T, Su C Y, Chang C S, Li H, Shi Y M, Zhang H, Lai C S, Li L J. Nano Lett., 2012, 12(3): 1538.
[117]

Lukowski M A, Daniel A S, Meng F, Forticaux A, Li L S, Jin S. J. Am. Chem. Soc., 2013, 135(28): 10274.
[118]

Zhan Y J, Liu Z, Najmaei S, Ajayan P M, Lou J. Small, 2012, 8(7): 966.
[119]

Liu Q, Li X L, He Q, Khalil A, Liu D B, Xiang T, Wu X J, Song L. Small, 2015, 11(41): 5556.
[120]

Shi Y M, Zhou W, Lu A Y, Fang W J, Lee Y H, Hsu A L, Kim S M, Kim K K, Yang H Y, Li L J, Idrobo J C, Kong J. Nano Lett., 2012, 12(6): 2784.
[121]

Huang H L, Chen L Q, Liu C H, Liu X S, Fang S X, Liu W P, Liu Y J. J. Mater. Chem. A, 2016, 4(38): 14577.
[122]

Tang Y J, Zhang A M, Zhu H J, Dong L Z, Wang X L, Li S L, Han M, Xu X X, Lan Y Q. Nanoscale, 2018, 10(18): 8404.
[123]

Zhang J W, Huang Y C, Li G, Wei Y G. Coord. Chem. Rev., 2019, 378: 395.
[124]

Huang Y C, Sun Y H, Zheng X L, Aoki T, Pattengale B, Huang J E, He X, Bian W, Younan S, Williams N, Hu J, Ge J X, Pu N, Yan X X, Pan X Q, Zhang L J, Wei Y G, Gu J. Nat. Commun., 2019, 10(1): 982.
[125]

Zhou D, Han B H. Adv. Funct. Mater., 2010, 20(16): 2717.
[126]

Tang Y J, Wang Y, Wang X L, Li S L, Huang W, Dong L Z, Liu C H, Li Y F, Lan Y Q. Adv. Energ. Mater., 2016, 6(12): 1600116.
[127]

Ghosh S, Azad U P, Singh A K, Singh A K, Prakash R. ChemistrySelect, 2017, 2(35): 11590.
[128]

Guo S W, Gao Z Y, Song J L, Bulin C K, Zhang B W. Chinese Journal of Inorganic Chemistry, 2019, 35(7): 1195.
[129]

(郭树旺, 高占勇, 宋金玲, 布林朝克, 张邦文. 无机化学学报, 2019, 35(7): 1195.)
[130]

Lu Y K, Guo X X, Yang L Y, Yang W F, Sun W T, Tuo Y X, Zhou Y, Wang S T, Pan Y, Yan W F, Sun D F, Liu Y Q. Chem. Eng. J., 2020, 394: 124849.
[131]

Hou J G, Zhang B, Li Z W, Cao S Y, Sun Y Q, Wu Y Z, Gao Z M, Sun L C. ACS Catal., 2018, 8(5): 4612.
[132]

Sun H H, Ji X Y, Qiu Y F, Zhang Y Y, Ma Z, Gao G G, Hu P G. J. Alloys Compd., 2019, 777: 514.
[133]

Hou Y, Pang H J, Zhang L, Li B N, Xin J J, Li K Q, Ma H Y, Wang X M, Tan L C. J. Power Sources, 2020, 446: 227319.
[134]

Liu S H, Xu Y X, Yang H. CN 109926069A. 2019.
[135]

(刘山虎, 许银霞, 杨浩. CN 109926069A. 2019.).

Funding

National Natural Science Foundation of China(21878336)

National Natural Science Foundation of China(22078227)

Shandong Provincial Natural Science Foundation, China(ZR2018MB035)

Applied Basic Research Projects of Qingdao(19-6-2-27-cg)

State Key Laboratory of Heavy Oil Processing(20CX02213A)

State Key Laboratory of Heavy Oil Processing(SKLOP201902005)

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