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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2024 , Vol. 36 >Issue 7: 998 - 1013

DOI: https://doi.org/10.7536/PC231008

Review

Stability of Transition Metal Phosphide in Catalytic Reactions

  • Bo Yang 1, 2, 3 ,
  • Gongxuan Lu , 1, * ,
  • Jiantai Ma 3
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  • 1 State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
  • 2 University of Chinese Academy of Sciences, Beijing 100049, China
  • 3 College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
* e-mail:

Received date: 2023-10-18

  Revised date: 2024-03-06

  Online published: 2024-07-01

Supported by

National Key R&D Program of China(2022YFB3803600)

National Natural Science Foundation of China(22272189)

National Natural Science Foundation of China(22102200)

National Natural Science Foundation of China(22302212)

Gansu Natural Science Foundation(22JR5RA105)

LICP Cooperation Foundation for Young Scholars(HZJJ23-01)

Chinese Academy of Sciences Talent Program youth Project B(E40149YB)

LICP Special Talent Program(E101A7SY)

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Abstract

To take advantage of renewable energy such as solar energy to split water to hydrogen is an important solution to address the environmental pollution and energy shortage crisis.The development of highly efficient,robust,and low-cost catalysts is the key to the production of green and clean hydrogen energy.Transition metal phosphides(TMPs),as kinds of composites that can replace noble metal catalysts,have attracted wide attention in the field of solar hydrogen production.However,the poor stability of TMPs under harsh reaction condition limits their large-scale application at industrial level.In this paper,the physicochemical properties,preparation methods,stability in catalytic reactions and stability improvement strategies of TMPs are reviewed.The reason for the decline of stability of TMPs is that they could react with H2O or O2,and TMPs are oxidized to metal oxides or hydroxides,Meanwhile the low valence phosphorus is oxidized to phosphate and dissolved in the reaction medium,resulting in the loss of phosphorus in TMPs.The stability of TMPs could be improved by means of tuning the polarity of support surface,coating protective layer,and doping foreign elements 。

Contents

1 Introduction

2 Physicochemical properties of transition metal phosphide

3 Synthesis of transition metal phosphide

4 Stability and stability enhancement strategies of transition metal phosphide in catalytic reactions

4.1 Stability of transition metal phosphide in reactions

4.2 Stability enhancement strategies of transition metal phosphide in reactions

5 Conclusion and outlook

Key words： transition metal phosphide; physicochemical properties; preparation method; stability enhancement strategies

Cite this article

Bo Yang , Gongxuan Lu , Jiantai Ma . Stability of Transition Metal Phosphide in Catalytic Reactions[J]. Progress in Chemistry, 2024 , 36(7) : 998 -1013 . DOI: 10.7536/PC231008

1 Introduction

fossil energy has made great contributions to the development of human society,but it is non-renewable,and a large number of combustion emissions will cause serious pollution to the ecological environment.These disadvantages drive people to find new renewable energy systems to replace traditional Fossil energy[1⇓⇓⇓⇓⇓⇓~8]。 In recent years,new energy sources such as solar energy,wind energy,water energy and nuclear energy have attracted great attention from science and industry because of their outstanding advantages such as green,clean,environmental protection and low carbon[9⇓⇓⇓⇓~14]。 Among the numerous new energy sources,solar energy has the characteristics of large total amount,wide distribution and renewability.However,solar energy also has the disadvantages of low energy density and discontinuity.Therefore,the efficient use of solar energy becomes difficult[15⇓⇓⇓⇓⇓⇓⇓⇓~24]。 At present,the main ways of solar energy utilization are:natural photosynthesis,photothermoelectric conversion,photovoltaic power generation and artificial photosynthesis.the electric energy generated by photovoltaic power generation technology is unstable and difficult to be connected to the grid.Therefore,it is one of the possible ways of energy conversion and utilization to convert the hard-to-use electric energy into green hydrogen energy storage by using photovoltaic and water electrolysis to produce hydrogen[25⇓~27]。 in addition,simulating photosynthesis In nature and directly using sunlight to catalyze water decomposition to produce hydrogen may be an important way to convert and utilize solar energy more efficiently[28⇓⇓⇓⇓⇓⇓⇓⇓⇓~38]。
Similar to photosynthesis in nature,which requires efficient invertase,efficient catalyst is the key to the conversion of solar energy into chemical energy[39⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~55]。 At present,the typical processes of solar water splitting into hydrogen energy(photocatalysis,photoelectrocatalysis and photovoltaic-electrocatalysis)all require efficient catalysts for hydrogen and oxygen evolution reactions[56⇓⇓⇓⇓~61]。 The noble metal catalyst has high activity and stability.However,its content in nature is rare,its price is high,and The cost of large-scale utilization is high.The study shows that it is feasible to replace precious metals with non-precious metal compounds[62⇓⇓⇓~66]。 transition metal compounds(transition metal carbides,transition metal phosphides,transition metal oxides,transition metal sulfides,etc.)have the potential to replace precious metal materials because of their simple synthesis,low cost and excellent catalytic activity[67][68][69][70]。 Among many transition metal compounds,transition metal phosphides have many advantages,such as rich crystal structure,variable coordination ratio between transition metal and P atom,and easy change and control of surface chemical state.Therefore,transition metal phosphides are widely used in photocatalytic and photoelectrocatalytic solar energy conversion reactions For hydrogen production.Most studies on transition metal phosphides have focused on how to improve their catalytic activity.for example,the catalytic activity of transition metal phosphides can be significantly improved by means of conductivity improvement,electronic structure optimization,heterojunction construction,heterogeneous atom doping,and interface regulation[68,71 ~72]。 However,the stability of transition metal phosphides in reaction media and catalytic conditions has not been well studied.It is of great significance to study the reasons for the stability decline of transition metal phosphides under different conditions and to propose strategies to enhance their stability for their large-scale and long-term applications。

2 Properties of transition metal phosphide

In the mid-18th century,Marggraf first synthesized zinc phosphide compounds,which opened the exploration of transition metal phosphides[73]。 However,in the following 200 years,transition metal phosphides have not attracted much attention.Until the 1950s,Sweeny et al.Found that nickel phosphide,a transition metal,as a heterogeneous catalyst,could realize the gas-phase reduction of nitrobenzene to aniline[74]。 Subsequently,it was found that transition metal phosphides have high catalytic activity in butadiene hydrogenation,oil hydrodesulfurization,hydrodenitrogenation and other reactions[75⇓⇓~78]。 In the 1990s,researchers found that transition metal phosphides can be used as electrocatalytic water splitting materials and electrochemical energy storage materials[79,80]。 Since the 21st century,transition metal phosphides have also been used in photocatalytic water splitting for hydrogen production and the elimination of pollutants in the environment[81,82]。
Transition metal phosphides can be regarded as compounds formed by phosphorus entering metal crystals,and their general chemical formula can be written as MxPy.Transition metal phosphides can be divided into metal-rich and phosphorus-rich transition metal phosphides according to the ratio of metal to phosphorus atoms in the transition metal phosphide.In the metal-rich transition metal phosphide MxPy(x>y),the electrons in the metal are not completely confined by phosphorus.Therefore,there is a M-M interaction,which leads to the metallic properties of transition metal phosphides[83]。 However,for phosphorus-rich transition metal phosphide MxPy(x<y),in which there is no M-M bond,the conductivity of the compound decreases.The excess phosphorus is mainly in the form of oligomers or clusters.For example,there are seven nickel phosphides with different Ni/P ratios,Ni3P,Ni12P5,Ni2P,Ni5P4,NiP,NiP2,and NiP3[84]。 With the decrease of Ni/P ratio,Ni in the compound is gradually diluted by P,the proportion of Ni—Ni bond decreases,the proportion of Ni—P bond increases,and the further increase of P content in the compound leads to the formation of P—P bond。
Phosphides with different metal phosphorus ratios have different spatial crystal configurations.With the change of coordination ratio of metal M and P,the crystal structure of transition metal phosphide changes regularly.In M2P-type transition metal phosphides,each P atom forms a tricapped trigonal prism with nine metal M atoms,and these trigonal prism polyhedra are attached to each other in a coplanar manner,forming a three-dimensional structure in space(Figure 1A )[85,86]。 in MP-type transition metal phosphides,such as CoP and FeP crystals,each P is coordinated by six M atoms,forming a distorted trigonal prism polyhedron.These triangular prisms are extended In space by sharing edges to form the structure of transition metal phosphides(Figure 1b)[87]。 The two P atoms in NiP are connected to each other by covalent bonds to form a dumbbell-shaped homoatomic junction.Each P2dumbbell is coordinated by eight Ni atoms,forming a distorted bicapped octahedral structure.The structure of NiP can be regarded as a crystal structure composed of multiple P2@Ni8polyhedra in space through the forms of common vertices and common edges(Figure 1C )[88]。 Further increasing the content of P in MxPyforms the crystal structure of MP2.In FeP2with CoP2,P-P interactions form P2dumbbells,each of which is surrounded by six M atoms,The octahedral structures of P2@M6are formed,and these octahedral structures are spread in space through edge-sharing and vertex-sharing to form the crystal structures of FeP2and CoP2(Fig.1 d).NiP2has two different crystal phases,cubic and monoclinic[88,89]。 The cubic NiP2consists of a three-dimensional network of regular Ni@P6octahedra connected by P—P bonds through common vertices(Fig.1 e).The monoclinic NiP2is composed of oblique Ni@P4quadrilateral units interconnected in the plane by P—P bonds to form a layered structure,while the P—P bonds connect the Ni@P4tetrahedra between these layers to form a spatial structure(Fig.1f )。
图1 (a)Fe2P、Co2P和Ni2P的晶体结构; (b)FeP、CoP的晶体结构; (c)NiP的晶体结构; (d)FeP2、CoP2的晶体结构; (e)立方NiP2的晶体结构; (f)单斜NiP2的晶体结构(Fe、Co、Ni: 蓝色；P：橙色); (g)过渡金属磷化物在Fermi能级处态密度的总结对比[86]; Ni2P的Ni 2p XPS (h), P 2p XPS (i) [90]

Fig. 1 Crystal structure of Fe2P, Co2P, and Ni2P(a); FeP and CoP (b); NiP (c); FeP2 and CoP2 (d); cubic NiP2 (e); monoclinic NiP2 (f) (Fe, Co, Ni: blue, P: orange); A summary of the DOS at the Fermi level for M2P and MP (g), Copyright©2018, Wiley[86]; Ni 2p XPS (h) and P 2p XPS (i) of Ni2P, Copyright©2008 American Chemical Society[90]

The electronegativity of P in transition metal phosphides is 2.19,which is higher than that of transition metals(Mn:1.55,Fe:1.83,Co:1.88,Ni:1.91,Cu:1.90,Mo:2.16).Due to the existence of poor electronegativity,part of the electrons in the transition metal are transferred to the phosphorus atom,forming a Mδ+Pδ-electronic configuration.The M-P bonding in most transition metal phosphides contains both covalent and ionic components.The greater the electronegativity difference between metal M and P,the higher the composition of the ionic bond in the formed M—P[90]。 When the electronegativity difference between M and P is small,the component of covalent bond in the formed M—P is higher[91]。 DFT calculations were used to study the electron density of States(DOS)of transition metal phosphides at the Fermi level,and the calculated DOS curves are shown in Figure 1G.For the M2P-type transition metal phosphide,the magnitude of DOS at the Fermi level is in the order of：Fe2P>Co2P>Ni2P.For MP-type transition metal phosphides,the DOS values at the Fermi level are lower than M2P and decrease in the order of FeP,CoP,NiP.Among the transition metal phosphides,Ni2P,FeP and CoP possess high catalytic activity,but their DOS values at Fermi level are in the middle position,which indicates that the moderate Fermi level DOS in the compounds is an important feature of high catalytic activity 。
Grosvenor et al.Used X-ray photoelectron spectroscopy(XPS)technique to study the chemical state of surface elements of transition metal phosphides[90,92]。 After removing the contaminating oxides on the surface of transition metal phosphides by sputtering,P 2p in MP and M2P(M=Fe,Co,Ni)shows a clear double peak of 2p3/2and 2p1/2,and its binding energy is smaller than that of elemental P.In M 2p,a sharp single peak appears,whose binding energy is slightly larger than that of the corresponding pure metallic elementary substance(Fig.1H~I).It shows that the charge transfer occurs between the transition metal and P atom.The binding energy of P 2p in transition metal phosphides decreases with the increase of the ionic component of the M—P bond.The binding energy of transition metal M increases with the increase of the ionic bond component in M—P.The shift of the binding energy position of metal and P in transition metal phosphides relative to that of elemental metal and P is related to the type of transition metal and the ratio of transition metal to P.In addition,because the surface of transition metal phosphide may be oxidized during the synthesis process to form metal phosphate compounds,there are still some challenges for the study of the surface of transition metal phosphide under reaction conditions[93,94][95⇓⇓~98]。

3 Synthesis of transition metal phosphide

The synthesis of transition metal phosphides can be divided into three categories according to the phase of the reaction process:liquid phase,gas-solid phase and solid phase.Liquid phase synthesis methods mainly include organic phosphorus source thermal injection method,hydrothermal method,solvothermal method and electrochemical deposition method.Organophosphorus source hot injection method is mainly used for the controlled synthesis of nanoscale transition metal phosphides with different morphologies and crystal structures.In the method,the transition metal phosphide is prepared by reacting a metal precursor with an organophosphorus source in a hot solvent under an inert atmosphere.The typical process for the synthesis of transition metal phosphides by hot injection of organophosphorus source is as follows:a transition metal source such as Ni2+is first reduced to nanoclusters of Ni0under the action of solvent oil amine(OAm).Trioctylphosphonium(TOP),as a strong ligand,adsorbs on the surface of Ni nanoparticles to form Ni-TOP complex.At elevated temperature,the P—C bond in TOP is broken to form a P atom.The P atom diffuses into the interior of the Ni nanocluster,while Ni diffuses into the outer layer.Because of the slow diffusion of P into the interior,hollow,nanostructured transition metal phosphides are formed(a phenomenon known as the Kirkendall effect)(Figure 2A )[94,99]。 There are many factors that can affect the crystal phase and morphology of the synthesized transition metal phosphides,such as the type of transition metal and P precursor,P/M ratio,reaction temperature,reaction time and solvent[100⇓⇓⇓⇓⇓~106]。 Although the transition metal phosphides synthesized by organophosphorus hot injection method have good crystal structure and controllable morphology,this method requires the use of expensive and toxic organic solvents,high reaction temperature,and complete avoidance of oxygen in the reaction process.These characteristics limit the application of solvothermal decomposition in the synthesis of transition metal phosphides.Hydrothermal or solvothermal methods can effectively control the morphology of synthesized transition metal phosphides.the main advantages of Hydrothermal synthesis of transition metal phosphides are that the precursors are relatively easy to obtain and relatively cheap,the synthesis process is simple,the product yield is high,and the morphology of the product is controllable.Hydrothermal or solvothermal reactions occur in high temperature,high pressure environments.the composition,structure and morphology of the synthesized transition metal phosphides are affected by the reaction conditions,such as the composition of the precursor,the ratio of P/M,the solvent and the temperature[107⇓~109]。 electrochemical deposition is also an important way to prepare transition metal phosphides.Compared with traditional synthesis techniques,electrochemical deposition has many advantages,such as direct reaction process,low energy consumption,short reaction time and simple experimental process.the electrolyte of the electrochemical deposition method is a solution containing transition metal ions,a phosphorus source precursor,a pH regulator and a conductivity regulator.the working electrode of electrochemical deposition method is a conductive carrier,such as nickel foam,Cu sheet,Ti sheet,carbon felt and so on.Lectrolysis is carry out by constant voltage,constant current or cyclic voltammetry,and transition metal phosphide is grown on that surface of the carrier by adjust parameters such as voltage,current and electrolysis time.transition metal phosphides with different morphologies can be prepared by electrochemical deposition,and the transition metal phosphides prepared by electrochemical deposition are closely combined with the support,which reduces the interfacial charge transfer resistance and effectively promotes the electrocatalytic activity[110⇓⇓⇓~114]。
图2 （a）液相法合成磷化镍纳米颗粒[100]，（b）气固法制备NiCoFeP纳米立方体过程示意图[139]，（c）固相法制备Co2P/N-HCR的过程示意图[148]

Fig. 2 (a) Scheme of synthesis of nickel phosphide nanoparticles, Copyright©2015 American Chemical Society[100], (b) Schematic illustration of the preparation of hollow porous NiCoFeP nanocubes, Copyright©2018 Wiley[139], (c) Schematic procedure for the fabrication of Co2P/N-HCR, Copyright©2017 Royal Society Chemistry[148]

Compared with the liquid phase reaction,the gas-solid method is more convenient for the synthesis of transition metal phosphides,which avoids the use of surfactants and organic solvents with high boiling points.The gas-solid synthesis of transition metal phosphides can be divided into three categories:the first category is the reduction of high-valence phosphate by H2,The second type is to synthesize transition metal phosphide by gas-solid phase reaction of low valence phosphate such as sodium hypophosphite(NaH2PO2),ammonia hypophosphite(NH4H2PO2)or elemental P vapor with transition metal precursor,and the third type is to synthesize transition metal phosphide by plasma-assisted method.In that reaction proces of reducing high-valence phosphate by use H2as a medium,phosphate and transition metal firstly react to obtain a transition metal phosphate compound.H2reduces transition metal phosphate complexes to phosphides at higher temperatures.The H2reduction method requires high reaction temperature,and the reduction by-product is water,which limits its application range[115⇓⇓~118]。 Therefore,a low temperature phosphating technology has been developed to phosphate transition metal precursors with phosphine produced by the decomposition of hypophosphite.Hypophosphite first decomposes to produce PH3gas,and then PH3reacts with various forms of transition metal precursors to obtain transition metal phosphides.The forms of transition metal precursors include transition metal salts,transition metal hydroxides,metal-organic framework compounds,etc.In general,the transition metal precursor is placed downstream of the tubular reactor and the hypophosphite is placed upstream of the reactor during the phosphating process.In the phosphating process,the PH3generated by the decomposition of hypophosphite reacts with the transition metal precursor downward with the gas flow to prepare the transition metal phosphide.Metal salts can be used as precursors to react with NaH2PO2to produce transition metal phosphides of different crystal forms[119,120]。 A self-supporting transition metal phosphide electrode can be prepared by reacting a transition metal hydroxide precursor supported on the surface of a current collector with a NaH2PO2[121⇓⇓~124]。 the transition metal phosphide on the surface of the current collector retains the nanostructure of the precursor,which makes the electrode have higher mass transfer and conductivity,so the catalytic activity is higher.Layered double hydroxides(LDHs)are used as precursors to prepare bimetallic phosphides after phosphating.For example,Ni-Co,Ni-Fe,Ni-Mn,Co-Fe,Co-Cu LDHs can be prepared by phosphating[125][126][127][128][129]。 Ni-Co multilayer LDH nanosheets were synthesized by hydrothermal method,and the Ni-Co bimetallic phosphide prepared by NaH2PO2phosphating retained the morphology of the precursor[130]。 Carbon layer-coated transition metal phosphides can be prepared by low temperature phosphating using metal-organic frameworks(MOFs)compounds as templates.For example,Fe-based MOFs,Co-based MOFs,Ni-based MOFs and bimetallic MOFs can be used to prepare the corresponding transition metal phosphides by phosphating[131][132][133][134]。 For example,CoNiP nanoboxes can be synthesized by phosphating CoNi-MOF as a metal precursor,and the transition metal active sites are uniformly dispersed on the surface of carbon materials with high specific surface area and multi-level pore structure[135]。 The synthesis of MOFs with phosphorus-containing organic ligands has corresponding advantages in The preparation of transition metal phosphides.For example,TMP@C materials were prepared by high temperature calcination using metal-organophosphorene framework(MOPF)as a template.The method does not introduce an additional phosphorus source,and is simpler and more convenient compared with a two-step phosphating method[136]。 Prussian blue(PBA)and its analogs,as a subtype of MOFs,have also been used to synthesize precursors of transition metal phosphides[137,138]。 Guo et al.Successfully synthesized hollow porous trimetal phosphide NiCoFeP nanocubes by chemical vapor deposition(CVD)phosphating NiCoFe PBA nanocrystals(Figure 2B)[139]。 plasma-assisted synthesis has The advantages of rapid reaction process,low reaction temperature,and can assist the synthesis of some metastable substances.Because the plasma-assisted synthesis takes place in the plasma-chemical vapor deposition chamber,the synthesis process is simple and safer.the plasma-assisted synthesis of phosphide has high uniformity[140]。 The plasma-assisted synthesis of transition metal phosphides can control the defects of the products,thereby changing their catalytic properties.For example,Ar plasma treatment was introduced to obtain P-rich vacancy and defect-rich Ni2P/Cu3P interface[141]。 A hierarchical porous NiCoxPy/CC catalyst was synthesized by a combination of electrochemical deposition and PH3plasma-assisted phosphating[142]。 CoPxfilms containing two phases of CoP and phosphorus-rich CoPx(P/Co>1)were synthesized by PH3plasma enhanced chemical vapor deposition using Co3O4as precursor[143]。
solid state ball milling technique can be used to synthesize a series of solid solutions,metastable crystals,quasicrystals,nanostructured compounds and amorphous alloys with equilibrium or non-equilibrium phase composition.Transition metal phosphides can be efficiently synthesized by solid phase ball milling.For example,nickel phosphide with different crystal phases can be prepared by high energy ball milling of Ni and P powders with the same stoichiometric ratio in Ar atmosphere to synthesize Ni-P precursor,and then annealing at different temperatures[144,145]。 High energy ball milling can also be used to synthesize cobalt phosphide materials[146,147]。 Liu et al.Used citric acid,cobalt acetate and diammonium hydrogen phosphate as carbon source,cobalt source and phosphorus source,respectively,to synthesize N-doped hollow carbon-encapsulated Co2P nanoparticle catalyst by ball milling and high temperature sintering method（Co2P/N-HCRs）（Fig.2 C )[148]。 the FeP material can also be prepared by a ball milling method,and The FeP nanoparticles can be prepared by mixing Fe powder and red phosphorus in a stoichiometric ratio and then grinding in an Ar atmosphere[149,150]。

4 Stability and Improvement Strategy of Transition Metal Phosphides in Catalytic Reaction

4.1 Stability of transition metal phosphide in reaction

A large number of studies have shown that transition metal phosphides have high catalytic activity,but their stability is relatively lacking[151,152]。 the stability of materials has an important influence On long-period applications.phosphorus content in transition metal phosphides is an important factor affecting their stability.metal-rich transition metal phosphides have high thermal stability due to their strong metal-phosphorus chemical bonds.However,its chemical stability is low due to its high surface metal content.on the contrary,the phosphorus-rich transition metal phosphide contains P-P dimers or clusters,and the excessive P-P polymer can be combined with the metal M as an encapsulant,so that the chemical stability of the phosphorus-rich transition metal phosphide is high.However,phosphorus-rich transition metal phosphides are unstable under heating conditions and can spontaneously decompose into metal-rich transition metal phosphides and elemental phosphorus at high temperatures,resulting in poor thermodynamic stability[84,153]。 Laursen et al.Found that the average heat of atom formation of nickel phosphide changed little with increasing P content in the bulk(Ni3P,Ni5P2,Ni12P5to Ni2P),However,the average heat of atom formation of Ni5P4,NiP2and NiP3decreases with the increase of P/Ni ratio when the P content further increases[154]。 Waxler et al.Used the difference between the chemical potentials of Ni and P(∆μNi&∆μP)to judge the stability of transition metal phosphides,and it can be seen that Ni2P and Ni5P4have higher stability than other nickel phosphides[96]。 Element doping can affect the stability of transition metal phosphides.the electronic structure of transition metal phosphide can be adjusted by metal,nonmetal or co-doping,which can not only control the catalytic activity of the material,but also improve its stability[155]。
the stability of transition metal phosphides is not only affected by their own properties,but also closely related to external factors such as reaction medium and reaction conditions.the stability of transition metal phosphides in the fields of hydrodeoxygenation(HDO),water treatment,electrocatalysis and photocatalysis was summarized.in HDO reaction,transition metal phosphides are easy to react with the reaction medium or catalytic products,resulting in changes in their structure and composition.Studies have shown that the water produced in the HDO reaction can attack the P in the transition metal phosphide to form phosphate,which binds to the surface active Ni sites and deactivates the catalyst[156]。 the surface hydrophobicity and pore structure of the support have a great influence on the activity and stability of the transition metal phosphide loaded on the surface.the higher the hydrophilicity of the support,the more serious the structural damage of the transition metal phosphide on the surface[157]。 Moon et al.Studied the stability of different types of support SiO2,ZrO2and activated carbon surface supported Ni2P catalysts in HDO of o-methoxyphenol[158]。 The stability of Ni2P/ZrO2and Ni2P/AC catalysts was high,while the HDO catalytic activity of Ni2P/SiO2catalyst decreased significantly.The more abundant hydroxyl groups and higher hydrophilicity on the surface of the SiO2support promote the oxidative reconstruction reaction of the surface Ni2P,resulting in the oxidation of the Ni2P catalyst to form phosphate during the reaction,resulting in the decrease of the activity of the catalyst.Different types of transition metal phosphides supported on the same SiO2support also showed different trends of catalytic activity decline.The decreasing trend of catalytic activity of Ni2P/SiO2,MoP/SiO2,and NiMoP/SiO2in anisole HDO was MoP>NiMoP>NiP,which may be attributed to the greater oxidation resistance of Niδ+than that of Moδ+[159]。
Significant deactivation also occurs in water treatment reactions catalyzed by transition metal phosphating.For example,the activity of FeP in the catalytic degradation of ibuprofen decreased gradually with the increase of the number of cycles.Feα+and Pβ-in FeP are oxidized to form Fe3+and PO43-during the activation of persulfate,and the dissolution of active components into the solution is the reason for the decline of catalyst activity[160]。 Choi et al.Found that CuxP catalyzes the reduction of O2to H2O2.The hydroxyl radical produced further was oxidized to Cu2+and PO43-and dissolved in the solution during the degradation of phenol,resulting in the gradual decrease of the activity of CuxP with the increase of cycles[161]。 According to Wang et al.,there are two main reasons for the decrease of the activity of CoP catalyst in the degradation of pollutants in activated peroxydisulfate water:(1)the surface active sites are occupied by sulfate and organic intermediates,which prevents the further reaction of CoP and peroxydisulfate;(2)CoP is continuously oxidized and consumed in the catalytic degradation of organic compounds[162]。 The cycle stability of FexP catalyst in the degradation and elimination of refractory pollutants in water environment is also related to the nature of pollutants.By increasing the amount of humic acid in the system,the reusability of the catalyst can be improved,but the problem of dissolution and activity decline of FexP in catalytic degradation can not be completely solved[163,164]。
Transition metal phosphides exhibit high electrochemical hydrogen evolution(HER)activity,but their stability in the reaction is not consistent.For example,Saadi et al.Found that the morphology and surface composition of electrodeposited CoP changed before and after HER reaction,but the overpotential of 24 H galvanostatic electrolysis only increased slightly,indicating that CoP has high stability in HER[111]。 Bard et al.Found that in acidic medium and inert Ar atmosphere,the surface of CoP can be oxidized during HER catalysis,and the oxide layer can be further corroded by acid and dissolved in solution,resulting in a decrease in HER current(Figure 3A)[165]。 Moreover,cathodic protection can not inhibit the oxidation and acid etching process of CoP at lower pH values.In the presence of O2and other oxidants,the rate of oxidation and acid etching on the surface of CoP is accelerated.Cobalt phosphide(Co2P@CP)supported on carbon cloth showed a slight increase in overpotential after HER stability test in acidic medium.However,the overpotential after the stability test in alkaline medium increased more significantly(Fig.3B).The catalysts of Co2P before and after HER in acidic and alkaline media were characterized.The surface composition and electrochemically active surface area of Co2P after the reaction in acidic medium did not change significantly,while the surface after the reaction in alkaline medium showed Co(OH)2（Fig.3D~f).This is due to the fact that Co2P dissolves Co and P stoichiometrically in acidic solution,while P dissolves in preference to Co in alkaline medium(Fig.3C )[166]。 Shao-Horn et al.Pointed out that after the CoP nanocatalyst was treated at a potential greater than 0.4 V,P in the CoP was oxidized to high-valence phosphate,which was dissolved from the surface of the material,and the P/Co ratio of the material decreased,resulting in a decrease in HER performance[167]。 Liu et al.Used in situ Raman spectroscopy to characterize the change of NiCoP in alkaline medium HER reaction,and the Raman spectrum of the catalyst after reaction showed PO43-stretching vibration peaks at 950 and 1150 cm-1,indicating that the surface of NiCoP was partially converted into NiCo phosphate[168]。 Kucernak et al.Found that the corrosion resistance of nickel phosphide in acidic medium HER process is related to the amount of phosphorus contained in it[169]。 The corrosion resistance of nickel phosphide increases with the increase of phosphorus content.The instability of NiP2in HER is related to its reaction with acid under non-oxidizing atmosphere,and the reaction equation is shown in Equation(1).In the presence of O2,transition metal phosphides react under acidic and alkaline conditions to form phosphate,and the reaction formula is(2),(3 )[170]。 the above analysis shows that the stability of transition metal phosphides in HER is related to many factors,such as Phosphorus content,pH value of solution,reaction atmosphere,overpotential and so on.phosphorus dissolution of transition metal phosphide in HER reaction is an important reason for the decrease of catalyst activity。
NiP2 + 6H+ → Ni2+ + 2PH3↑ (g)
MP2 + H2SO4 + 2H2O + 3O2 → MSO4 + 2H3PO4
MP2 + 6KOH + 3O2 → M(OH)2 + 2K3PO4 + 2H2O
图3 (a) CoP 电极HER电解不同时间后的LSV曲线[165]; (b) Co2P@CP在0.5 mol/L H2SO4 和1 mol/L KOH溶液中2000次LSV扫描前后的HER极化曲线, (c) ICP-OES分析稳定性测试后溶液中Co和P浓度, (d) 新制Co2P@CP、(e) 酸性溶液中稳定性测试后Co2P@CP、(f) 碱性溶液中稳定性测试后Co2P@CP的SEM图片[166]；(g) CoMnP在1.0 mol/L KOH溶液中的OER极化曲线(LSV), 起始曲线(黑色)，经过200 次CV循环(红色)，经过500 次CV循环(蓝色)。CoMnP催化剂经过OER电解前后的Co 2p3/2 (h)和P 2p (i)的XPS谱图[172]; (j) Cu3P-3% CNT 光催化分解水机理，(k) Cu3P-3% CNT 的循环产氢曲线[177]；(l) CoP/NC的循环产氧曲线，(m) CoP/NC光催化反应后的HRTEM图像[183]; (n) NixP在水中暗态条件下的析氢活性, (o) ICP-OES检测暗态反应后Ni和P的浓度[184]

Fig. 3 (a) Series of HER LSVs for the CoP electrode after HER electrolysis for different time, Copyright©2017 American Chemical Society[165]; (b) HER polarization curves (normalized by ECSA of Co2P@CP before (solid lines) and after 2000 LSV sweeps (dashed lines) in 0.5 mol/L H2SO4 and 1 mol/L KOH; (c) ICP-OES analysis of Co and P ion dissolution concentration in the electrolyte during the stability tests and the corresponding nonelectrochemical control immersion experiments, SEM images of as-synthesized Co2P@CP (d), Co2P@CP after stability test in acid (e), and Co2P@CP after stability test in alkaline (f), Copyright©2018 American Chemical Society[166]; (g) OER polarization curves for CoMnP nanoparticles, in 1.0 M KOH initially (black), after 200 (red) and 500 CV sweeps (blue) vs RHE. (h) Co 2p3/2, (i) P 2p XPS spectra for CoMnP nanoparticles before (top) and after (bottom) electrolysis for 10 h, Copyright©2016, American Chemical Society[172]; (j) Possible photocatalytic H2 production mechanism with Cu3P-3% CNT, (k) Repeated cycles of hydrogen production with Cu3P-3% CNT, Copyright©2018 American Chemical Society[177]; (l) Time courses of O2 evolution using CoP/NC catalyst in five repetitive examinations, (m) HRTEM images of recovered CoP/NC after the light reaction, Copyright©2019 Elsevier[183]; (n) Hydrogen evolution activity of NixP synthesized with different nP/nNi in the dark, (o) Concentration of Ni and P measured by ICP-OES in NixP reaction system after 3 h reaction in the dark, Copyright©2022 Chinese Journal of Inorganic Chemistry. [184]

Transition metal phosphides are susceptible to oxidative reconstruction during the electrocatalytic water splitting oxygen evolution(OER)reaction.the in situ conversion of CoP into an active site for oxygen evolution occurred in the OER.the catalyst after in situ conversion has a nano-network dispersion structure composed of phosphate-rich and separated Co oxides/hydroxides,and some phosphorus-containing substances are dissolved into the solution during the in situ conversion process,resulting in a decrease in the P/Co ratio,and the catalyst after in situ conversion shows high OER stability[171]。 The LSV overpotential of CoMnP for OER after multiple anodic CV cycles was elevated(Figure 3G).XPS proved that the surface of CoMnP was oxidized to MPOxand MOxin the OER reaction,while a high concentration of phosphate ions was detected in the solution after the reaction.The loss of phosphate during surface oxidative reconstruction is an important reason for the decrease of OER activity(Fig.3 H~I )[172]。 Costa et al.Found that the overpotential of Fe0.2Ni0.8P2under OER galvanostatic conditions first increased,and then remained stable for a long time[170]。 The Fe0.2Ni0.8P2is oxidized and reconstituted into iron-containing nickel hydroxide with low crystallinity in the OER reaction,and the formed amorphous mixed metal hydroxide can catalyze the OER reaction and maintain stable activity for a long time.The in situ oxidative reconstruction of Co0.6Fe0.4P into Co-Fe oxide/hydroxide is an 8-electron transfer oxidation reaction,as shown in Equation(4).The current decay of the catalyst was 7.6%during 120 H of potentiostatic electrolysis.XPS characterization after reaction showed that the peaks of Co-P and Fe-P on the surface of Co0.6Fe0.4P after OER reaction almost disappeared,while the peaks of Co-O and Fe-O increased in intensity[173]。
Co0.6Fe0.4P+11OH-→Co0.6Fe0.4OOH + PO43- + 8e- + 5H2O
transition metal phosphides as cocatalysts can accelerate the separation and transfer of surface charge on semiconductors and reduce the surface reaction overpotential,so they are widely used in photocatalytic water splitting for hydrogen production.A large number of studies have shown that Transition metal phosphide modified semiconductor catalysts have good stability in photocatalytic water splitting reaction[174⇓~176]。 However,it has also been pointed out that the photocatalyst of transition metal phosphide modified semiconductor is unstable in the photocatalytic water splitting reaction.The hydrogen evolution performance of Cu3P/CNT in the system with eosin as the photosensitizer and triethanolamine as the sacrificial reagent decreased by 20%after four photocatalytic cycles,and the researchers believed that the reason for the decrease in activity was that the Cu3P co-catalyst on the surface of carbon nanotube(CNT)peeled off during the reaction(Fig.3j–K )[177]。 The photocatalytic hydrogen production stability test of the g-C3N4-Co2P-K2HPO4system showed that the activity of the catalytic system decreased by 25%after five cycles.The exfoliation of the Co2P co-catalyst from the surface of the g-C3N4nanosheets is responsible for the decrease in catalytic activity[178]。 The stability of CoP/CeVO4photocatalyst for photocatalytic water splitting was studied in the system of triethanolamine as sacrificial reagent and eosin Y as photosensitizer.The results showed that the catalytic activity decreased significantly in the second cycle.The reason for the decrease of photocatalytic activity is the consumption of photosensitizer eosin Y in the reaction.The photocatalytic water splitting activity of the material was restored by adding an additional photosensitizer to the system[179]。 In the process of photocatalytic hydrogen production from water by Cu3P@CoP p-n heterojunction with triethanolamine as sacrificial reagent and eosin Y as photosensitizer,although 10 mg photosensitizer was added after each cycle,the photocatalytic hydrogen production efficiency of the system still decreased by 13.7%after four cycles.The photocorrosion of materials is an important reason for the decrease of photocatalytic activity of the system[180]。 Transition metal phosphides have also been used as promoters for photocatalytic oxygen production.1.0%-CoP/Al:STO photocatalyst was prepared by modifying Al-doped SrTiO3with CoP cocatalyst.The photocatalyst showed excellent photocatalytic water splitting activity,and the activity of the catalyst decreased slightly after three cycles[181]。 The anatase/rutile heterojunction TiO2was modified by Pt and CoP co-catalysts to realize photocatalytic water splitting.The CoP co-catalyst enhanced the photocatalytic oxygen generation performance of the TiO2heterojunction,and the photocatalytic water splitting activity of the material was maintained for 9 H[182]。 CoP embedded in nitrogen-doped carbon material(CoP/NC)catalyzes water splitting to produce oxygen under the condition of using[Ru(bpy)3]2+as a photosensitizer and S2O82-as an electron acceptor sacrificial reagent,and the activity of CoP/NC decreases slightly after five photocatalytic cycles(Fig.3l).The characterization showed that the surface of CoP after the photocatalytic oxygenic reaction was oxidized to amorphous CoOx,forming a core-shell structure of CoP@CoOx(Figure 3M )[183]。 Yang et al.Directly dispersed NixP powder in H2O to verify the stability of the material in aqueous solution under dark conditions[184,185]。 It was found that NixP spontaneously reacted with H2O,and a Ni(OH)xlayer was formed on the surface.At the same time,Pδ-is oxidized to phosphate ion and dissolved in water,while H2O is reduced to H2（(Fig.3 n~o).Further study shows that the similar corrosion law also exists in CoxP in water.Although some studies have shown that the activity of transition metal phosphide cocatalyst modified photocatalysts decreases in the photocatalytic water splitting cycle reaction and the long period process,the reason for this phenomenon is still insufficient.There is still a lack of research on the long-term stability of transition metal phosphide cocatalysts in photocatalytic water splitting reaction 。

4.2 Strategies for Improving the Stability of Transition Metal Phosphides in Reactions

the lack of stability of transition metal phosphides in aqueous medium may become an important obstacle to their large-scale application.Poor stability leads to a rapid decrease in the catalytic efficiency of the catalyst.in order to stabilize the catalytic conversion rate,fresh catalyst replenishment or frequent regeneration of the catalyst is needed,which will lead to a significant increase in the cost of long-term application.Therefore,it is of great significance to improve the stability of the catalyst in the reaction medium and reaction conditions.Researchers have proposed different strategies to enhance the stability of transition metal phosphides in different reactions。
In HDO,it is very necessary to enhance the resistance of transition metal phosphides to oxygen-containing substances such as H2O under reaction conditions because of the large amount of oxygen-containing compounds in both the feedstock and the hydrorefined product.Different methods,such as doping modification,modification of support properties,and coating,can be used to enhance the stability of transition metal phosphides in HDO.The surface of Ni2P was partially sulfurized by carbon disulfide(CS2)to form NiPS phase,and the surface NiPS layer could prevent the reaction of Ni2P with H2O to form oxidized nickel and phosphate,and the HDO catalytic stability of the catalyst treated by CS2was significantly improved after an induction period[186]。 Mondal et al.Prepared nanohybrid CoxP@POP of porous organic polymer(POP)encapsulated CoxP particles by solid-state phosphating method,and the 3D intercrosslinked porous N-doped polymer matrix encapsulation enhanced the stability of CoxP in HDO[187]。 Song et al.Wrapped a hydrophobic TiO2layer on the surface of Al2O3support,and the hydrophobic TiO2layer enhanced the water corrosion resistance of the catalyst in HDO reaction[188]。 Compared with the Ni2P/Al2O3,the Ni2P/Al2O3@TiO2exhibited higher HDO activity and stability,indicating that the hydrophobic TiO2layer is beneficial to enhance the stability of the Ni2P and maintain the HDO activity of the catalyst(Figure 4A).In order to prevent the decrease of catalyst activity in water,the affinity of the support for polar substances should be reduced.The surface polarity of the Ni2P/SiO2catalyst was changed by copolymerizing tetraethoxysilane and organosilane.The Ni2P/SiO2-50MTES prepared by copolymerizing tetraethyl orthosilicate with the same amount of methyltriethoxysilane shows enhanced stability[189]。
The leaching of transition metal phosphides in wastewater treatment seriously affects the catalytic activity and its long cycle life.To enhance the stability of materials in water treatment reactions,coupling with carbon-containing supports is a possible strategy.A vacuum-packed rGO@FexP/C heterogeneous catalyst was prepared by tightly wrapping FexP/C with intercrosslinked reduced graphene oxide(rGO)nanosheets.The rGO coating layer with a suitable thickness reduces the etching dissolution of iron in the FexP/C,greatly enhances the stability of the catalyst,and has little effect on the activity of the catalyst(Fig.4 B~C )[190]。 Sun et al.Used g-C3N4to wrap the CuxP to enhance its stability in the photo-Fenton reaction.The pyridine nitrogen in the g-C3N4can form a stable coordination with the Cu(I)site in the CuxP,which reduces the destruction of the double catalytic center in the CuxP during the reaction[191]。 The CuxP/g-C3N4catalyst thus exhibits enhanced photo-Fenton stability.The FeP modified Fe monoatom-graphene oxide(FeP/Fe1-GO)exhibited high cyclic catalytic stability in the visible-light-irradiated/H2O2(Vis/H2O2)system,and the degradation efficiency of tetracycline could still maintain 93.6%after 100 cycles.The rapid charge transfer on the surface of FeP/Fe1-GO and the accelerated cycling rate of Fe3+/Fe2+are the reasons for the high activity of the system in the long period and multiple cycles[192]。
The surface of transition metal phosphides is transformed into metal hydroxides in HER,accompanied by the dissolution of phosphate ions,which eventually leads to the decline of the catalytic performance of the materials.Therefore,it is necessary to take appropriate measures to stabilize the active sites on the surface of transition metal phosphides.At present,the strategies to improve the stability of materials in HER are:coating method and sacrificial reagent method.The electrochemical deposition method was used to wrap a layer of Ni(OH)2armor on the surface of CoP,and the Ni(OH)2protective layer not only reduced the P dissolution in the CoP core,but also promoted the activation and decomposition of H2O on the electrode surface,so that the CoP@Ni(OH)2core-shell structure hybrid had high HER activity and stability at the same time(Fig.4D∼f )[193]。 The core-shell structure of CoP@Co(OH)xwas constructed by in situ electrochemical method,and the HER stability of the catalyst was enhanced by the Co(OH)xprotective layer[194]。 Hu et al.Designed a multilayer structure electrode of ultrathin NiFe LDH layer wrapped CoMoP nanosheets,and the strong coupling effect between the two-dimensional porous material and the ultrathin nanosheet array reduced the dissolution of P element in the reaction process of the material and enhanced the stability[195]。 In addition,carbon-based material encapsulation has also been used to improve the stability of transition metal phosphides in HER.Chai et al.Used ultrathin hollow nitrogen-doped carbon nanospheres to encapsulate bimetallic Ni2P/Co2P hybrid,and the corrosion of the composite under extreme conditions was reduced,and the HER stability of the catalyst was enhanced[196]。 Zhou et al.Prepared nitrogen and phosphorus-doped carbon-coated Co-Co2P nanoparticles(Co-Co2P@NPC/rGO)catalysts loaded on the surface of graphene[197]。 Both the encapsulation of N and P doped C and the fixation of reduced graphene oxide enhance the stability of the Co-Co2P.The stability of Co-Co2P@NPC/rGO in 0.5 mol/L H2SO4medium at HER current density of 1000 mA·cm-2can be maintained for 20 H.In addition to the coating method,researchers have also developed sacrificial reagent methods to improve the stability of transition metal phosphides in HER.The Mn sacrificial reagent slows down the irreversible oxidation of CoPxto Co(OH)2,CoOx,and CoPxOyin discontinuous HER.The introduction of Mn makes the oxidation potential of CoPxshift to negative,while the doped Mn itself,as a sacrificial reagent,is oxidized and converted into Mn(OH)2[198]。
Transition metal phosphides are first oxidized and reconstructed in OER,forming high-valence metal oxides or oxyhydroxides,while low-valence Pδ-are oxidized to phosphates,which are partially dissolved in the electrolyte,resulting in a decrease in catalytic activity.In order to enhance the stability of transition metal phosphides in OER,researchers have proposed the strategy of coating metal hydroxide protective layers on their surfaces.Although it has been shown that the high-valence metal oxide/hydroxide shell formed by in situ surface oxidation of transition metal phosphides in OER can form a stable core-shell structure with the transition metal phosphide core,It is beneficial to improve the overall stability of the catalyst,but some studies have shown that coating the metal hydroxide layer on the surface of the transition metal phosphide can further promote the oxidative reconstruction of the material during the reaction and enhance its stability under the reaction conditions[171]。 For example,Zhang et al.Employed electrochemical pretreatment of Ni-CoP/Co2P@NC to coat CoOOH nanosheets on its surface[199]。 The current density of the catalyst coated with CoOOH on the surface of Ni-CoP/Co2P@NC did not decrease in the long-term OER test,and the morphology and surface element chemical composition of the catalyst after reaction did not change significantly compared with the newly prepared sample.Wu et al.Used an electrochemical method to deposit FeOOH on the surface of CoPxto construct a CoPx@FeOOH core-shell catalyst[200]。 the catalyst showed good cycle and long time potentiostatic stability and resistance to chloride ion chemical corrosion.Zhou et al.Electrodeposited a NiFe LDH layer on The surface of CoNiP nanosheets to prepare a core-shell catalyst with a hierarchical structure[201]。 Due to the strong interaction between the two phases,the CoNiP@NiFe-LDH electrode showed a very small amount of P dissolution in OER,and the overpotential of the catalyst remained stable during galvanostatic electrolysis for 500 H(Fig.4G~H).in addition,Yang et al.Used carbon layers or derived carbon hybrid layers to improve the stability of transition metal phosphides in OER[202]。 For example,the core-shell catalyst was prepared by coating Co/CoP nanoparticles with N and P-doped carbon nanotubes,and the current density of the catalyst decreased by only 10%after 9 H reaction,and the stability exceeded RuO2.The use of amorphous carbon-coated transition metal phosphide nanoparticles can enhance the stability of the catalyst in OER,and the durability of the carbon-coated catalyst in OER can be improved[203]。 The Co2P nanoparticles were embedded into N-doped porous carbon to prepare the Co2P@N-C catalyst,and the strong anchoring effect between the porous carbon layer with high specific surface area and Co2P enhanced the stability of the catalyst,and the OER activity of the Co2P@N-C electrode could be maintained for 24 H[204]。
图4 (a) 新制和反应后Ni2P/Al2O3、Ni2P/Al2O3@TiO2 催化剂的表面结构[188]; (b) rGO@FexP/C的制备示意图，(c) FexP/C和rGO@FexP/C 阴极的循环实验[190]; (d) CoP/Ni(OH)2 在HER大电流电解过程中快速分解水，减少P损失示意图，(e) CoP/Ni(OH)2-15 min和CoP 在电解过程中溶液中P的浓度和(f) 电解70 h的计时电势曲线[193]；(g) CoNiP@NiFe LDH 多级结构纳米阵列合成示意图，(h) CoNiP@NiFe LDH-100 NSAs的计时电势曲线[201]；(i) CTF-CoP-1% 和物理负载CTF/CoP-1%的循环测试，(j) CTF-CoP-1%的表面电荷转移和光催化产氢机理[206]；(k) Co K-边(左)和Ni K-边(右)的小波变换(WT) 谱，(l) NiCo-Pi/g-C3N4的光催化循环产氢测试[207]

Fig. 4 (a) Surface structures of the fresh and spent Ni2P/Al2O3 and Ni2P/Al2O3@TiO2 catalysts, Copyright© 2016 Elsevier[188]; (b) Schematic illustration of the preparation steps of rGO@FexP/C, (c) Cycling experiments using FexP/C and rGO@FexP/C cathodes, Copyright©2021 Wiley[190]; (d) Schematic drawing of CoP/Ni(OH)2 with fast water dissociation, reduced phosphorus loss and large current density, (e) Phosphorus content in solution of CoP/Ni(OH)2-15 min and CoP under 100 mA cm-2, (f) Chronopotentiometric profile of the CoP/Ni(OH)2-15 min catalysts at 400 mA cm-2 for 70 h, Copyright©2021 Elsevier[193]; (g) Schematic illustration for the synthesis of CoNiP@NiFeLDH hierarchical arrays, (h) Chronopotentiometric measurements at 50 mA·cm-2 of CoNiP@NiFe LDH-100 NSAs for 500 h, Copyright©2018 American Chemical Society[201]; (i) Recycling test of CTF-CoP-1% and physically immobilized CTF/CoP-1%，(j) The schematic diagram of charge transfer and the possible mechanism for photocatalytic H2 evolution of CTF-CoP-1%, Copyright© 2022 The Royal Society of Chemistry[206]; (k) Wavelet transform (WT) spectra for the k2-weighted Co K-edge (Left) and Ni K-edge (Right), (l) Cycling tests of photocatalytic H2 generation over NiCo-Pi/g-C3N4 at 410 nm, Copyright© 2020 The Royal Society of Chemistry [207]

In order to improve the stability of transition metal phosphides in photocatalytic reactions,the strategy of chemical bond anchoring was proposed.The transition metal phosphide and the photocatalysis semiconductor material are connected by utilizing a chemical bond,the transition metal phosphide on the surface of the semiconductor is stabilized due to the effect of the firm chemical bond,and meanwhile,photogenerated electrons are promoted to be transferred to the transition metal phosphate cocatalyst along the chemical bond,so that the stability of the photocatalyst is enhanced.3D NiCoP nanoparticles were immobilized on the surface of 2D g-C3N4by constructing Co—N and Ni—N chemical bonds.The photocatalytic hydrogen generation stability of the NiCoP/g-C3N4heterojunction can be maintained for 60 H[205]。 CoP and covalent organic framework(CTF)are chemically bonded by in-situ self-assembly and annealing,which is beneficial to enhance the cycle stability of the catalyst.CTF-CoP showed almost no loss of activity after 4 cycles of photocatalysis.However,the activity of the catalyst simply supported on the surface of CTF decreased significantly due to factors such as CoP dissolution and surface polymerization(Fig.4 I~J)[206]。 Chen et al.Utilized an ultrasound-assisted method to introduce NiCo-Pi into the interlayer of g-C3N4[207]。 The XAS characterization proves that NiCo-Pi and g-C3N4are bonded together by means of chemical bonds.The strong chemical bonding force between the cocatalyst and the semiconductor makes the NiCo-Pi/g-C3N4highly resistant to photocorrosion,and its photocatalytic hydrogen production stability exceeds 20 H(Fig.4K~l).The L-cysteine is used as a bridge to connect the NiCoP cocatalyst and the CdS semiconductor in the form of a covalent bond,and the L-cysteine-coated NiCoP cocatalyst is tightly immobilized on the CdS surface.The photocatalytic stability of 40 wt%L-cysteine-encapsulated CdS reached 192 H[208]。 in a word,the stability of transition metal phosphides in catalytic reactions can be effectively improved and the potential of materials in long-period applications can be enhanced by means of carrier surface polarity regulation,protective shell wrapping,stable chemical bond connection and doping.A summary of various methods to improve the stability of transition metal phosphides is shown in Table 1。
表1 Summary of Strategies for Enhancing the Stability of Transition Metal Phosphides in Reactions

Table 1 Summary of stability enhancement strategies for transition metal phosphide in reactions

Stability Enhancement strategy Advantages Disadvantages Ref
Polarity modification of support surface Pretreatment of Ni2P by CS2 to form NiPS hydrophobic layer Decrease the affinity of support towards polar substances;
The deactivation of catalyst is relieved		 The catalytic efficiency might be influenced 186
Coating hydrophilic Al2O3 support with hydrophobic TiO2 layer 188
Copolymerizing TEOS with organsilanes to adjust surface polarity 189
Coating with protective layer Coating CoxP with porous organic polymer The TMP’s surface was modified with protective layer: construction of protective layer could avoid the loss of P in TMPs, construction of abundant interfaces between TMPs core and shell will enhance catalytic activity The preparation process is complex; the overcoating of pro- tective layer could decrease activity. 187
Coating FexP/C with cross-linking rGO nanosheet 190
CoP was electrodeposited with Ni(OH)2 armor layer to inhibit the loss of P 193
The strong interaction between ultrathin NiFe LDH nanosheet and 2D porous CoMoP enhances the stability 195
CoNiP was modified with NiFe LDH to construct a hierarchical core-shell structure to enhance electrocatalytic activity and durability 201
Co2P was embedded in N-doped porous carbon to enhance activity and stability via synergistic effect 204
Connection of TMPs with semiconductor via strong metal- support Interactions Embedding NiCoP nanocluster on the surface of g-C3N4 via Co-N and Ni-N bond The intimate interaction between cocatalyst and photo-responsive semiconductor would exhibit better durability in photocatalytic reaction; the charge transfer is accelerated via the chemical bond The preparation of strong interaction between support and cocatalyst/ photocatalyst is more complex than traditional supported catalyst 205
in situ self-assembly method was adopted to decorate CoP nanoparticles on covalent organic frameworks 206
The intimate covalent bond between NiCoP and CdS due to L-cysteine display enhanced stability 208
Doping with foreign elements Co-deposition of Mn onto the CoPx electrode could shift the electrode potential below the equilibrium potential of Co(OH)2, preventing the oxidation of CoPx Lower shift the corrosion potential of TMPs; regulate the electro-structure of catalyst.
 The protection effect depends on doping elements 198

5 Conclusion and prospect

Transition metal phosphides have high catalytic activity and have the potential to replace precious metals in the catalytic conversion and utilization of new energy sources.However,it has poor stability in the reaction medium,which affects the life of the catalyst.Enhancing the stability of transition metal phosphides is of great significance for their practical applications.In this pap,that stability of transition metal phosphides and the main strategy to enhance the stability are summarized.The main reason for the poor stability of transition metal phosphides is that they can be oxidized by H2O or O2to form metal hydroxides or phosphate compounds,and some of the phosphate on the surface is dissolved in the reaction medium,resulting in the continuous decrease of P content in transition metal phosphides during the reaction.At present,hydrophilic modification of support,coating oxide or carbon material protective layer,adding sacrificial reagent or enhancing the interaction between transition metal phosphide and support are commonly used methods to improve its stability 。
Based on the previous understanding of the stability and improvement methods of transition metal phosphides,the stability mechanism of transition metal phosphides under reaction conditions is discussed and analyzed in depth,and the development of new stability improvement strategies is an important research direction of this kind of materials in the future.the development of stable transition metal phosphides and their derivatives is of great significance for their practical application in the catalytic conversion and utilization of new energy and related fields.We believe that the possible ways to further enhance the stability of transition metal phosphides are as follows:(1)to achieve a balance between the activity and stability of the catalyst by changing the preparation method of the material and adjusting the crystal structure and bulk composition of the synthesized transition metal phosphide;(2)preparing a multi-component transition metal phosphide alloy and a derivative thereof by introducing an external element for doping modification,wherein the introduction of the doping element can change the coordination mode of the transition metal and phosphorus,thereby improving the stability of the material;(3)a more stable protective shell is wrapped on the surface of the transition metal phosphide.Due to the different hydrophilicity and hydrophobicity of different types of shell materials and their binding force with transition metal phosphides,the protection performance is different.Therefore,it is necessary to develop new protective shell materials to enhance the stability of transition metal phosphides in catalytic reactions。

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