Elementary substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst and preparation method thereof

Abstract

The invention relates to an elementary substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst. A preparation method comprises the following steps: 1) dissolving a metal salt A, urea and ammonium fluoride in deionized water to obtain a mixed solution B; 2) performing hydrothermal reaction on the mixed solution B and a carrier to obtain a primary sample 1; 3) performing high-temperature calcination on the primary sample 1 in a mixed atmosphere of hydrogen and argon to obtain a primary sample 2; and 4) putting the preliminary sample 2 into a noble metal compound C solution for vacuum impregnation, taking out the sample after impregnation, and drying to obtain the catalyst. According to the scheme, the metal salt A is used as a metal source of a simple substance / alloy, the metal salt A is subjected to hydro-thermal synthesis to form a metal hydroxide and then subjected to high-temperature calcination reduction, the metal salt A is calcined to form the simple substance / alloy, then the simple substance / alloy is soaked in the precious metal compound solution C to form a metal oxyhydroxide, and meanwhile precious metal single atoms / clusters are anchored; the prepared catalyst is high in activity, and the preparation method is simple.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical technology, and in particular to a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst and a preparation method thereof. Background Art

[0002] Hydrogen (H2), with its high energy density and zero carbon emissions, is considered an ideal clean energy carrier to replace fossil fuels and alleviate energy crises and environmental issues. The current mainstream steam reforming hydrogen production process is constrained by its associated carbon dioxide emissions and unsustainable nature. Electrocatalytic water splitting is a promising route to produce high-purity hydrogen with zero carbon emissions, providing an effective path for the sustainable production of high-purity hydrogen. However, its high energy consumption severely limits its large-scale application. In conventional water electrolysis systems, the hydrogen evolution reaction (HER) occurs at the cathode, while the oxygen evolution reaction (OER) occurs at the anode. Compared to the efficient HER process, the OER involves a complex four-electron transfer mechanism with sluggish kinetics and a high theoretical potential (1.23 V vs. RHE). This requires a higher overpotential to drive the reaction, significantly reducing the overall energy conversion efficiency of the system. To address this bottleneck, the strategy of replacing the OER with the oxidation of thermodynamically advantageous small molecules (such as urea, hydrazine hydrate, ammonia, 5-hydroxymethylfurfural, and ethanol) offers a new approach to overcome the technical barriers of hydrogen production by electrolysis.

[0003] In recent years, to enhance the electrocatalytic activity of non-noble metal-based catalysts for small molecule oxidation reactions, diverse design strategies have been systematically developed, including interface engineering, doping engineering, strain engineering, defect engineering, and morphology manipulation. Catalyst systems, represented by transition metal nitrides, sulfides, phosphides, oxides / oxyhydroxides, and alloys, have made significant progress. However, limited by the inherent activity of non-noble metals, researchers often introduce noble metal components such as platinum (Pt), ruthenium (Ru), palladium (Pd), and gold (Au) to break through the upper limit of catalytic performance. Notably, atomic-scale dispersion of noble metal catalysts has become a key research direction in this field, as it maximizes atomic utilization efficiency and optimizes cost-effectiveness. Studies have shown that the synergistic effect of noble metal single atoms and support materials can significantly enhance catalytic activity. Despite this, the development of efficient and stable catalysts that meet the requirements of industrial-scale green hydrogen production remains a significant challenge. Of particular note, noble metal clusters with multi-site structures offer more flexible electronic control capabilities, and their unique electronic structure can generate multifunctional active sites. These breakthroughs have enabled single-atom / cluster-modified catalysts to demonstrate broad application prospects in the fields of water electrolysis and small molecule oxidation. Therefore, the development of highly active and stable noble metal single-atom / cluster heterojunction catalysts is of great importance. Summary of the Invention

[0004] To this end, the present invention provides a highly active and stable dual-functional catalyst for water electrolysis and small molecule oxidation, a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst and a preparation method thereof.

[0005] To achieve the above objectives, the inventors provide a method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst, which comprises the following steps:

[0006] 1) dissolving metal salt A, urea and ammonium fluoride in deionized water to obtain a mixed solution B;

[0007] The metal salt A is one or more of the following: iron salt, nickel salt, copper salt, cobalt salt, zinc salt, titanium salt, chromium salt, manganese salt, calcium salt, vanadium salt, gallium salt, germanium salt, strontium salt, yttrium salt, zirconium salt, niobium salt, cadmium salt, indium salt, tin salt, antimony salt, hafnium salt, tantalum salt, tungsten salt, rhenium salt, thallium salt, lead salt, bismuth salt, lanthanum salt, cerium salt, praseodymium salt, neodymium salt, samarium salt, europium salt, gadolinium salt, terbium salt, dysprosium salt, holmium salt, erbium salt, ytterbium salt or thulium salt;

[0008] The feed ratio of the metal salt A, urea and ammonium fluoride is 2.5-20:3-5:1;

[0009] 2) adding the mixed solution B and the pretreated support into a reactor for hydrothermal reaction at a temperature of 80-280° C. for a reaction time of 6-48 hours. After the reaction is completed, the mixture is cooled to room temperature, the reaction solution in the reactor is removed and filtered, and the filter cake is washed and dried to obtain a preliminary sample 1;

[0010] The ratio of the input mass of the metal salt A to the surface area of ​​the pretreated support is 54-370:1 mg / cm 2 ;

[0011] 3) placing the preliminary sample 1 prepared in step 2) in a calcining furnace, introducing a mixture of hydrogen and argon, wherein the volume fraction of hydrogen in the mixture is 5-50%, heating the mixture to 200-1000° C. at a heating rate of 3-20° C. / min, and calcining the mixture at high temperature for 1.5-6 hours to obtain a preliminary sample 2;

[0012] 4) placing the preliminary sample 2 into a solution of the noble metal compound C and vacuum impregnating it for 10-180 minutes; after the impregnation, removing the sample and drying it to obtain a single substance / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst;

[0013] The noble metal compound C is one or a mixture of two of the following: silver salt, gold salt, iridium salt, platinum salt, rhodium salt, ruthenium salt, osmium salt or palladium salt;

[0014] When the noble metal compound C is a mixture of two noble metal compounds, the concentration ratio of the two metal compounds in the noble metal compound C solution is 1:1-5.

[0015] The present invention adopts the above scheme, using metal salt A as the metal source of the elemental / alloy. A metal hydroxide is first hydrothermally synthesized and then calcined at high temperature to reduce the metal salt A. The metal salt A is calcined to form a single substance or alloy. The metal hydroxide is then vacuum impregnated in a precious metal compound solution to form a metal oxyhydroxide. This simultaneously anchors the precious metal single atoms / clusters, resulting in a single substance / alloy-metal oxyhydroxide-anchored precious metal single atom / cluster heterojunction catalyst. This single substance / alloy-metal oxyhydroxide-anchored precious metal single atom / cluster heterojunction catalyst exhibits high catalytic activity and stability.

[0016] The elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention has the following advantages:

[0017] (1) Strain effect: In the heterostructure designed in this invention, a metal alloy core-noble metal shell composite system is constructed. The significant chemical composition difference and lattice constant mismatch between the two components are exploited to induce a non-uniform lattice strain field at the interface. This strain effect significantly changes the electronic structure of the noble metal shell through compression / stretching, effectively regulating the adsorption free energy of key reaction intermediates at the active sites on the catalyst surface.

[0018] (2) Synergistic effect: By precisely constructing metal alloys, metal hydroxide oxycarriers, and noble metal single atom / cluster heterojunctions, a strong electronic coupling effect is formed between the multiple components, and the electron transfer rate is improved. This charge redistribution characteristic simultaneously optimizes the charge transfer dynamics and surface wetting characteristics of the catalytic system, and increases the density of active sites through the interface confinement effect. The multi-component synergistic mechanism breaks through the functional limitations of a single material, achieves a synergistic enhancement of the conductivity stability reaction kinetics, and provides theoretical guidance for the construction of an efficient and stable composite catalytic system.

[0019] (3) Interface electron regulation mechanism: The band structure differences between different components at the heterojunction interface induce significant Fermi level dislocations, forming directional charge transfer channels through the interface states. Simultaneously, electrons undergo spatial redistribution, constructing an electron cloud structure with gradient characteristics in the interface region. This charge reconstruction effect not only induces local lattice distortion of surface atoms, but also achieves precise optimization of the adsorption configuration of reaction intermediates by regulating the d-band orbital symmetry of the noble metal.

[0020] The present invention has a simple preparation process. The catalyst prepared by the present invention exhibits good HER, OER, HzOR, and UOR catalytic performance in 1.0 mol / L potassium hydroxide, 1.0 mol / L potassium hydroxide + 0.5 mol / L hydrazine hydrate, and 1.0 mol / L potassium hydroxide + 0.5 mol / L urea electrolytes, respectively. Due to the simple preparation method and high activity of the catalyst prepared by the present invention, it has strong competitiveness in fields such as water electrolysis for hydrogen production and small molecule oxidation.

[0021] Furthermore, the support in step 1) is a metal support or a non-metal support, wherein the metal support is one of the following: metal mesh, metal sheet, metal wire, metal foil, alloy mesh, alloy sheet, or alloy wire. The selection of a metal or non-metal support material is intended to create an ideal self-growth environment for the elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst, thereby significantly improving the catalyst's stability and catalytic activity.

[0022] Furthermore, the metal mesh is one of the following: nickel mesh, copper mesh, titanium mesh, cobalt mesh or iron mesh; the alloy mesh is nickel-iron mesh or nickel-molybdenum mesh; all of which can provide a stable support structure;

[0023] The metal sheet is one of the following: nickel sheet, cobalt sheet, copper sheet, iron sheet or titanium sheet, which can be selected according to specific performance requirements;

[0024] The alloy sheet is one of the following: nickel-cobalt sheet, nickel-copper sheet, iron-copper sheet, nickel-iron sheet, stainless steel sheet, nickel-molybdenum sheet or nickel-chromium sheet. These alloy sheets combine the advantages of multiple metals and improve comprehensive performance;

[0025] The metal wire is one of the following: nickel wire, cobalt wire, copper wire, iron wire, aluminum wire or titanium wire to meet the needs of different application scenarios;

[0026] The alloy wire comprises one of the following: nickel-iron wire or nickel-molybdenum wire, both of which have excellent electrical conductivity and heat resistance;

[0027] The metal foil is one of the following: nickel foil, cobalt foil, copper foil, iron foil, zinc foil or titanium foil; these foils have excellent ductility and covering properties and are suitable for uniform distribution of the catalyst layer.

[0028] The above-selected metal and alloy materials, as carriers, can provide an ideal substrate for the growth of elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalysts, thereby enhancing their stability and catalytic activity;

[0029] The non-metallic support is one of the following: carbon black tubes, carbon nanotubes, carbon fiber sheets, activated carbon fibers, graphene blocks, porous carbon blocks, carbon cloth, carbon felt, glass fiber mesh, layered graphite, or expanded perlite. Each of these materials has its own unique characteristics, providing a diverse substrate for elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalysts, helping to improve performance and stability.

[0030] Furthermore, in the step 3), after the preliminary sample 1 is placed in a calcining furnace for calcination, if the metal salt A contains only one metal salt, the metal salt A is calcined to form a simple substance, and the formed simple substance is one of the following: Fe, Ni, Cu, Co, Zn, Ti, Cr, Mn, Ca, V, Ga, Ge, Sr, Y, Zr, Nb, Cd, In, Sn, Sb, Hf, Ta, W, Re, Tl, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm; if the metal salt A contains two or more metal salts, it is calcined to form an alloy.

[0031] <h2 style=";text-align:left;direction:ltr">FeNi,F eCo,FeZn,FeTi,FeCr,FeMn,FeV,FeN b,FeCd,FeIn,FeSn,FeSb,FeHf,FeTa,FeW,FeRe,FeTl,FePb,FeBi,CuZn,C uNi,CuCo,CuTi,CuCr,CuMn,CuV,CuNb,CuCd,CuIn,CuSn,CuSb,CuHf,CuTa ,CuW,CuRe,CuTl,CuPb,CuBi,CuGa,CuGe,CuY,CuZr,NiCo,NiZn,NiTi,NiCr ,NiMn,NiV,NiNb,NiCd,NiIn,NiSn,NiSb,NiHf,NiTa,NiW,NiRe,NiTl,NiP b,NiBi,CoZn,CoTi,CoCr,CoMn,CoV,CoNb,CoCd,CoIn,CoSn,CoSb,CoHf,Co Ta,CoW,CoRe,CoTl,CoPb,CoBi,ZnTi,ZnCr,ZnMn,ZnV,ZnNb,ZnCd,ZnIn,Z nSn,ZnSb,ZnHf,ZnTa,ZnW,ZnRe,ZnTl,ZnPb,ZnBi,TiCr,TiMn,TiV,TiNb,T iCd,TiIn,TiSn,TiSb,TiHf,TiTa,TiW,TiRe,TiTl,TiPb,TiBi,CrMn,CrV,CrNb,CrCd,CrIn,CrSn,CrSb,CrHf,CrTa,CrW,CrRe,CrTl,CrPb,CrBi,MnV ,MnNb,MnCd,MnIn,MnSn,MnSb,MnHf,MnTa,MnW,MnRe,MnTl,MnPb,MnBi,VN b,VCd,VIn,VSn,VSb,VHf,VTa,VW,VRe,VTl,VPb,VBi,NbCd,NbIn,NbSn,NbS b,NbHf,NbTa,NbW,NbRe,NbTl,NbPb,NbBi,CdIn,CdSn,CdSb,CdHf,CdTa,C dW,CdRe,CdTl,CdPb,CdBi,InSn,InSb,InHf,InTa,InW,InRe,InTl,InPb,I nBi,SnSb,SnHf,SnTa,SnW,SnRe,SnTl,SnPb,SnBi,SbHf,SbTa,SbW,SbRe, SbTl,SbPb,SbBi,HfTa,HfW,HfRe,HfTl,HfPb,HfBi,TaW,TaRe,TaTl,TaPb,TaBi, WRe, WTl, WPb, WBi, ReTl, RePb, ReBi, TlPb, TlBi, PbBi, LaCe, LaNi, LaCo, LaCu, LaZn, CeNi, CeCo, CeCu , CeZn, FeNiCo, FeNiZn, FeCoZn, FeTiCr, FeCrMnV, CuNiZn, CuNiCo, CuZnTi, CuCrMn, NiCoZn, NiCoTi, NiZnCr. ,

[0032] Furthermore, in the step 4), the single atom / cluster formed is one of the following: Ag, Au, Ir, Pt, Rh, Os, Ru, Pd, AgAu, AgIr, AgPt, AgRh, AgRu, AgOs, AgPd, AuIr, AuPt, AuRh, AuRu, AuOs, AuPd, IrPt, IrRh, IrRu, IrOs, IrPd, PtRh, PtRu, PtOs, PtPd, RhRu, RhOs, RhPd, RuOs, RuPd, OsPd.

[0033] Furthermore, the carrier is pretreated by immersing the untreated carrier material in anhydrous ethanol, a 2.0 mol / L hydrochloric acid solution, and deionized water, followed by rinsing two to three times, each rinsing lasting 20 to 30 minutes. This pretreatment step is intended to thoroughly remove the oxide layer and other impurities on the carrier surface, ensuring its surface purity and providing an ideal substrate for subsequent catalyst growth.

[0034] Further, the metal iron salt in the metal salt A in step 1) is one of the following: ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous oxalate, ferric sulfate, ferric chloride, ferric nitrate, ferric phosphate, ammonium ferric citrate, ferrous acetate, ferrous carbonate, ferrous bromide, ferric iodide, ferric perchlorate, ferric thiocyanate, ferric stearate, ferric benzoate;

[0035] The metal manganese salt in the metal salt A in step 1) is one of the following: manganese chloride, manganese sulfate, manganese nitrate, manganese carbonate, manganese acetate, manganese oxalate, manganese phosphate, manganese bromide, manganese iodide, manganese fluoride, manganese perchlorate, manganese citrate, manganous sulfate, manganous acetate, manganous oxalate, manganous hydrogen phosphate, manganese pyrophosphate, manganese metasilicate;

[0036] The metal nickel salt in the metal salt A in step 1) is one of the following: nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, nickel oxalate, nickel carbonate, nickel phosphate, nickel potassium cyanide, nickel thiocyanate, nickel fluoride, nickel bromide, nickel iodide, nickel perchlorate, nickel sulfamate, nickel formate, nickel propionate, nickel acetylacetonate, nickel tartrate, nickel citrate, nickel stearate, nickel benzoate;

[0037] The copper metal salt in the metal salt A in step 1) is one of the following: copper sulfate, copper nitrate, copper chloride, copper acetate, copper oxalate, copper carbonate, copper phosphate, cuprous cyanide, cuprous iodide, copper bromide, copper perchlorate, copper silicate, basic copper carbonate, copper stearate, copper benzoate, copper citrate, copper acetylacetonate, copper formate, copper thiocyanate;

[0038] The metal cobalt salt in the metal salt A in step 1) is one of the following: cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt phosphate, cobalt bromide, cobalt iodide, cobalt sulfide, cobalt fluoride, cobalt perchlorate, cobalt citrate, cobalt stearate, cobalt laurate, cobalt benzoate, ammonium cobalt chloride, ammonium cobalt sulfate, ammonium cobalt nitrate, cobalt hydrogen phosphate, cobaltous acetate;

[0039] The metal zinc salt in the metal salt A in step 1) is one of the following: zinc sulfate, zinc nitrate, zinc chloride, zinc carbonate, zinc phosphate, zinc bromide, zinc fluoride, zinc iodide, zinc perchlorate, zinc acetate, zinc oxalate, zinc citrate, zinc stearate, zinc benzoate, zinc formate, zinc thiocyanate, zinc ammonium sulfate, zinc acetylacetonate;

[0040] The metal titanium salt in the metal salt A in step 1) is one of the following: titanium sulfate, titanium chloride, titanium nitrate, titanyl sulfate, potassium fluorotitanate, titanium oxalate, titanium phosphate, titanium acetate, titanium acetylacetonate, titanium formate, titanium citrate, titanium bromide, titanium iodide, titanium carbonate;

[0041] The metal chromium salt in the metal salt A in step 1) is one of the following: chromium sulfate, chromium chloride, chromium nitrate, chromium acetate, chromium oxalate, chromium phosphate, chromium carbonate, chromium bromide, chromium iodide, chromium fluoride, chromium perchlorate, chromium acetylacetonate, chromium citrate, chromium stearate, chromium benzoate, chromium formate, chromous sulfate, chromous chloride, chromium thiocyanate;

[0042] The metal manganese salt in the metal salt A in step 1) is one of the following: manganese sulfate, manganese nitrate, manganese chloride, manganese carbonate, manganese phosphate, manganese acetate, manganese oxalate, manganese fluoride, manganese bromide, manganese iodide, manganese perchlorate, manganese acetylacetonate, manganese citrate, manganese stearate, manganese benzoate, manganese formate, manganese thiocyanate, and ammonium manganese sulfate;

[0043] The metal calcium salt in the metal salt A in step 1) is one of the following: calcium carbonate, calcium phosphate, calcium sulfate, calcium chloride, calcium fluoride, calcium bromide, and calcium iodide;

[0044] The metal vanadium salt in the metal salt A in step 1) is one of the following: ammonium vanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadyl sulfate, vanadyl oxalate, vanadium tetrachloride, vanadium trichloride, sodium vanadate, potassium vanadate, vanadium pentachloride, vanadium sulfate, vanadium phosphate;

[0045] The metal zinc salt in the metal salt A in step 1) is one of the following: zinc sulfate, zinc nitrate, zinc chloride, zinc carbonate, zinc phosphate, zinc bromide, zinc fluoride, zinc iodide, zinc perchlorate, zinc acetate, zinc oxalate, zinc citrate, zinc stearate, zinc benzoate, zinc formate, zinc thiocyanate, zinc silicate, zinc molybdate, zinc tungstate, zinc ammonium sulfate, zinc acetylacetonate;

[0046] The metal gallium salt in the metal salt A in step 1) is one of the following: gallium sulfate, gallium nitrate, gallium chloride, gallium phosphate, gallium acetate, gallium oxalate, gallium bromide, gallium fluoride, gallium iodide, gallium perchlorate, and gallium citrate;

[0047] The metal germanium salt in the metal salt A in step 1) is one of the following: germanium chloride, germanium sulfate, germanium nitrate, germanium fluoride, germanium bromide, germanium iodide, germanium acetate, germanium oxalate, germanium phosphate, and germanium thiocyanate;

[0048] The metal strontium salt in the metal salt A in step 1) is one of the following: strontium sulfate, strontium nitrate, strontium chloride, strontium carbonate, strontium phosphate, strontium bromide, strontium fluoride, strontium iodide, strontium acetate, strontium oxalate, and strontium chromate;

[0049] The metal yttrium salt in the metal salt A in step 1) is one of the following: yttrium sulfate, yttrium nitrate, yttrium chloride, yttrium phosphate, yttrium acetate, yttrium oxalate, yttrium fluoride, yttrium carbonate;

[0050] The metal zirconium salt in the metal salt A in step 1) is one of the following: zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium phosphate, zirconium acetate, zirconium oxalate, zirconium fluoride, zirconium carbonate, zirconium oxychloride;

[0051] The metal niobium salt in the metal salt A in step 1) is one of the following: niobium chloride, niobium sulfate, niobium nitrate, niobium oxalate, niobium phosphate, potassium fluoroniobate, and niobium acetate;

[0052] The metal cadmium salt in the metal salt A in step 1) is one of the following: cadmium sulfate, cadmium nitrate, cadmium chloride, cadmium acetate, cadmium carbonate, cadmium phosphate, cadmium bromide, cadmium fluoride, cadmium iodide, cadmium thiocyanate;

[0053] The metal indium salt in the metal salt A in step 1) is one of the following: indium sulfate, indium nitrate, indium chloride, indium phosphate, indium acetate, indium fluoride, indium bromide, indium iodide, indium oxalate, indium perchlorate;

[0054] The metal tin salt in step 1) is one of the following: stannous chloride, stannous sulfate, stannous nitrate, stannous acetate, tin chloride, tin sulfate, tin nitrate, tin phosphate, tin oxalate, tin fluoride;

[0055] The metal antimony salt in the metal salt A in step 1) is one of the following: antimony chloride, antimony sulfate, antimony nitrate, antimony fluoride, antimony bromide, antimony iodide, antimony acetate, and antimony phosphate;

[0056] The metal hafnium salt in the metal salt A in step 1) is one of the following: hafnium chloride, hafnium sulfate, hafnium nitrate, hafnium phosphate, hafnium acetate, hafnium fluoride, hafnium oxalate, and hafnium oxychloride;

[0057] The metal tantalum salt in the metal salt A in step 1) is one of the following: tantalum chloride, tantalum sulfate, tantalum nitrate, tantalum oxalate, tantalum phosphate, tantalum acetate, tantalum fluoride, tantalum oxychloride;

[0058] The metal tungsten salt in the metal salt A in step 1) is one of the following: sodium tungstate, ammonium tungstate, tungsten chloride, tungsten sulfate, tungsten nitrate, tungsten fluoride, tungsten acetate;

[0059] The metal rhenium salt in the metal salt A in step 1) is one of the following: potassium perrhenate, rhenium chloride, rhenium sulfate, rhenium nitrate, rhenium fluoride, rhenium bromide, rhenium acetate, and rhenium thiocyanate;

[0060] The metal thallium salt in the metal salt A in step 1) is one of the following: thallium sulfate, thallium nitrate, thallium chloride, thallium acetate, thallium carbonate, thallium bromide, thallium iodide, thallium fluoride, thallium oxalate;

[0061] The metal europium salt in the metal salt A in step 1) is one of the following: europium fluoride, europium nitrate;

[0062] The metal bismuth salt in the metal salt A in step 1) is one of the following: bismuth nitrate, bismuth sulfate, bismuth chloride, bismuth citrate, bismuth oxalate, bismuth acetate, bismuth fluoride, bismuth iodide, bismuth subnitrate;

[0063] The metal lanthanum salt in the metal salt A in step 1) is one of the following: lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthanum acetate, lanthanum phosphate, lanthanum oxalate, lanthanum fluoride, lanthanum carbonate, lanthanum citrate;

[0064] The metal cerium salt in the metal salt A in step 1) is one of the following: cerium sulfate, cerium nitrate, cerium chloride, cerium acetate, cerium oxalate, cerium fluoride, cerium phosphate, cerium carbonate, cerium citrate;

[0065] The metal praseodymium salt in the metal salt A in step 1) is one of the following: praseodymium nitrate, praseodymium sulfate, praseodymium chloride, praseodymium acetate, praseodymium fluoride, praseodymium oxalate, praseodymium phosphate, and praseodymium carbonate;

[0066] The metal neodymium salt in the metal salt A in step 1) is one of the following: neodymium nitrate, neodymium sulfate, neodymium chloride, neodymium acetate, neodymium fluoride, neodymium oxalate, neodymium phosphate, and neodymium carbonate;

[0067] The metal samarium salt in the metal salt A in step 1) is one of the following: samarium nitrate, samarium sulfate, samarium chloride, samarium acetate, samarium fluoride, samarium oxalate, samarium phosphate, and samarium carbonate;

[0068] The metal europium salt in the metal salt A in step 1) is one of the following: europium nitrate, europium sulfate, europium chloride, europium acetate, europium fluoride, europium oxalate, europium phosphate, and europium carbonate;

[0069] The metal gadolinium salt in the metal salt A in step 1) is one of the following: gadolinium nitrate, gadolinium sulfate, gadolinium chloride, gadolinium acetate, gadolinium fluoride, gadolinium oxalate, gadolinium phosphate, and gadolinium carbonate;

[0070] The metal terbium salt in the metal salt A in step 1) is one of the following: terbium nitrate, terbium sulfate, terbium chloride, terbium acetate, terbium fluoride, terbium oxalate, terbium phosphate, or terbium carbonate;

[0071] The metal dysprosium salt in the metal salt A in step 1) is one of the following: dysprosium nitrate, dysprosium sulfate, dysprosium chloride, dysprosium acetate, dysprosium fluoride, dysprosium oxalate, dysprosium phosphate, and dysprosium carbonate;

[0072] The metal holmium salt in the metal salt A in step 1) is one of the following: holmium nitrate, holmium sulfate, holmium chloride, holmium acetate, holmium fluoride, holmium oxalate, holmium phosphate, and holmium carbonate;

[0073] The metal erbium salt in the metal salt A in step 1) is one of the following: erbium nitrate, erbium sulfate, erbium chloride, erbium acetate, erbium fluoride, erbium oxalate, erbium phosphate, and erbium carbonate;

[0074] The metal ytterbium salt in the metal salt A in step 1) is one of the following: ytterbium nitrate, ytterbium sulfate, ytterbium chloride, ytterbium acetate, ytterbium fluoride, ytterbium oxalate, ytterbium phosphate, and ytterbium carbonate;

[0075] The metal thulium salt in the metal salt A in step 1) is one of the following: thulium nitrate, thulium sulfate, thulium chloride, thulium acetate, thulium fluoride, thulium oxalate, thulium phosphate, and thulium carbonate.

[0076] The above types of metal salts A are selected because they cover most of the elements in the fourth period and the conclusions obtained are universal.

[0077] Furthermore, the silver compound of the precious metal compound C in step 3) is one of the following: silver nitrate, silver sulfate, silver chloride, silver fluoride, silver bromide, silver iodide, silver acetate, silver carbonate, silver phosphate, silver oxalate, silver citrate, silver thiocyanate, silver cyanide, and silver perchlorate;

[0078] The gold compound in the precious metal compound C in step 3) is one or two of the following: gold trichloride, potassium aurous cyanide, sodium gold thiosulfate, gold nitrate, gold sulfate, gold acetate, gold bromide, gold fluoride, gold iodide, and gold thiocyanate;

[0079] The iridium compound in the noble metal compound C in step 3) is one of the following: iridium chloride, iridium nitrate, iridium sulfate, iridium fluoride, iridium bromide, iridium acetate, iridium oxalate, chloroiridic acid, ammonium hexachloroiridate, iridium thiocyanate;

[0080] The platinum compound in the precious metal compound C in step 3) is one of the following: chloroplatinic acid, potassium chloroplatinite, platinum nitrate, platinum sulfate, platinum chloride, platinum fluoride, platinum bromide, platinum acetate, platinum oxalate, platinum cyanide, ammonium hexachloroplatinate;

[0081] The rhodium compound in the precious metal compound C in step 3) is one of the following: rhodium chloride, rhodium nitrate, rhodium sulfate, rhodium fluoride, rhodium bromide, rhodium acetate, rhodium oxalate, ammonium chlororhodiumate, rhodium trichloride hydrate, rhodium thiocyanate;

[0082] The ruthenium compound in the precious metal compound C in step 3) is one of the following: ruthenium chloride, ruthenium nitrate, ruthenium sulfate, ruthenium fluoride, ruthenium bromide, ruthenium acetate, ruthenium oxalate, ammonium chlororuthenate, ruthenium trichloride hydrate, ruthenium thiocyanate;

[0083] The osmium compound in the noble metal compound C in step 3) is one of the following: osmium chloride, osmium nitrate, osmium sulfate, osmium fluoride, osmium bromide, osmium acetate, osmium oxalate, ammonium chloroosmate, and osmium thiocyanate;

[0084] The palladium compound in the noble metal compound C in step 3) is one of the following: palladium chloride, palladium nitrate, palladium sulfate, palladium fluoride, palladium bromide, palladium acetate, palladium oxalate, palladium cyanide, ammonium chloropalladate, and sodium tetrachloropalladate.

[0085] Furthermore, in step 4), the concentration of the noble metal compound C solution is 0.5-4 mg / L.

[0086] The present invention also discloses a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst, which is prepared by the above-mentioned preparation method.

[0087] The above technical solution offers the following advantages over existing technologies: The present invention utilizes this solution, using metal salt A as the metal alloy source. Metal hydroxide is first generated, followed by high-temperature calcination and reduction. Metal salt A is calcined to form a single substance / alloy. This is then vacuum impregnated in a noble metal salt solution C to form a metal oxyhydroxide, simultaneously anchoring noble metal single atoms / clusters. This results in a single substance / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst. The catalyst prepared by the present invention features a simple preparation method and high activity, making it highly competitive in applications such as water electrolysis and small molecule oxidative coupled hydrogen production. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 The XRD pattern of the element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 of the present invention;

[0089] Figure 2 This is a Raman graph of the elemental / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 of the present invention;

[0090] Figure 3 TEM data of the elemental / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 of the present invention;

[0091] Figure 4 AC-TEM data of the elemental / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 of the present invention;

[0092] Figure 5 The linear sweep voltammetry (LSV) curve data of hydrogen evolution of the catalyst prepared in Example 1 of the present invention and a 20 wt.% commercial Pt / C catalyst in a 1.0 mol / L potassium hydroxide solution;

[0093] Figure 6 Tafel slope curve data of the catalyst prepared in Example 1 of the present invention and a 20 wt.% commercial Pt / C catalyst in a 1.0 mol / L potassium hydroxide solution;

[0094] Figure 7 Linear sweep voltammetry (LSV) curve data for oxygen evolution of the catalyst prepared in Example 1 of the present invention and a 40 wt.% commercial RuO2 / C catalyst in a 1.0 mol / L potassium hydroxide solution;

[0095] Figure 8 Tafel slope curve data for the catalyst prepared in Example 1 of the present invention and a 40 wt.% commercial RuO2 / C catalyst in a 1.0 mol / L potassium hydroxide solution;

[0096] Figure 9 LSV curve data for hydrazine hydrate oxidation of the catalyst prepared in Example 1 of the present invention and a 20 wt.% commercial Pt / C catalyst in a mixed solution of 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate;

[0097] Figure 10 These are Tafel slope curve data of the catalyst prepared in Example 1 of the present invention and a 20 wt.% commercial Pt / C catalyst in a mixed solution of 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate.

[0098] Figure 11 LSV curve data for hydrazine hydrate oxidation of the catalyst prepared in Example 1 of the present invention and a 40 wt.% commercial RuO2 / C catalyst in a mixed solution of 1.0 mol / L potassium hydroxide and 0.5 mol / L urea;

[0099] Figure 12 These are the Tafel slope curve data of the catalyst prepared in Example 1 of the present invention and a 20 wt.% commercial RuO2 / C catalyst in a mixed solution of 1.0 mol / L potassium hydroxide and 0.5 mol / L urea. DETAILED DESCRIPTION

[0100] In order to explain the technical content, structural features, achieved objectives and effects of the technical solution in detail, the following is a detailed description in conjunction with specific embodiments and accompanying drawings.

[0101] Example 1

[0102] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0103] (1) The untreated nickel mesh was rinsed with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water three times, each time for 20 minutes (surface area 10 cm 2 );

[0104] (2) 0.292 g of nickel nitrate, 0.292 g of cobalt nitrate, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0105] (3) Mixed solution B was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 120° C. The reaction was kept warm for 6 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0106] (4) The primary sample 1 obtained in step (3) was placed in a tube furnace, a mixture of hydrogen and argon (hydrogen accounting for 15% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 400°C at a rate of 5°C / min, and the temperature was kept at this temperature for 2 hours for high-temperature calcination to obtain a primary sample 2.

[0107] (5) 7.5 mL of 1.5 mg / L chloroplatinic acid solution and 7.5 mL of 1.5 mg / L iridium chloride solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 60 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0108] The element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in this example was subjected to XRD detection, and the XRD pattern of the detection is shown in FIG. Figure 1 .

[0109] from Figure 1 The X-ray diffraction (XRD) standard charts corresponding to the catalyst prepared in this example are Co:PDF#15-0806 and Ni:PDF#03-1051, indicating the formation of a nickel-cobalt alloy. No peaks of PtIr crystals or NiCoOOH were observed. This indicates that the size of the PtIr single atom / cluster crystal particles is below the detection limit of XRD analysis, and the NiCoOOH exists in an amorphous form.

[0110] The element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 was subjected to Raman spectroscopy (Raman) detection, and the detection data are shown in FIG. Figure 2 , 400-500cm -1 and 500-600cm -1 Raman bands appeared in the range, which may be due to the bending vibration of Ni, Co-O, indicating the formation of NiCoOOH.

[0111] The catalyst prepared in Example 1 was examined by transmission electron microscopy (TEM). Figure 3 It can be seen that the lattice fringes of NiCo(111) and PtIr(111) are 0.209nm and 0.220nm respectively. The catalyst prepared in Example 1 was tested by spherical aberration transmission electron microscopy (AC-TEM). The specific test results are shown in Figure 4 , it can be seen that the PtIr singleton is anchored on NiCoOOH (PtIr SA ) and PtIr clusters (PtIr C ).

[0112] Combined with the above XRD, Raman, TEM and ACTEM results, this example successfully prepared a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst.

[0113] Example 2

[0114] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0115] (1) The untreated copper mesh was rinsed with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water three times, each time for 20 minutes (surface area 10 cm 2 );

[0116] (2) 0.403 g of ferric nitrate, 0.256 g of zinc molybdate, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0117] (3) Mixed solution B was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 120° C. The reaction was kept warm for 6 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0118] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixed gas of hydrogen and argon (hydrogen accounting for 15% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 450°C at a rate of 3°C / min, and the temperature was kept at this temperature for 3 hours for high-temperature calcination to obtain a primary sample 2.

[0119] (5) 7.5 mL of 1 mg / L ruthenium chloride solution and 2 mL of 1.5 mg / L iridium chloride solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 120 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0120] Example 3

[0121] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0122] (1) The untreated titanium mesh was rinsed with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water three times, each time for 20 minutes (surface area 10 cm 2 );

[0123] (2) Dissolve 0.313 g of nickel iodide, 0.182 g of copper acetate, 0.6 g of urea, and 0.186 g of ammonium fluoride in 40 mL of deionized water to obtain a mixed solution B;

[0124] (3) Mixed solution B was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 140° C. The reaction was kept warm for 10 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0125] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixed gas of hydrogen and argon (hydrogen accounting for 35% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 500°C at a rate of 10°C / min, and the temperature was kept at this temperature for 2 hours for high-temperature calcination to obtain a primary sample 2.

[0126] (5) 7.5 mL of 2 mg / L palladium chloride solution and 7.5 mL of 3 mg / L iridium acetate solution were mixed to obtain a noble metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 30 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored noble metal single atom / cluster heterojunction catalyst.

[0127] Example 4

[0128] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0129] (1) The untreated nickel wire was rinsed with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water three times, each time for 20 minutes (surface area 10 cm 2 );

[0130] (2) 0.320 g of copper sulfate, 0.315 g of vanadium tetrachloride, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0131] (3) Mixed solution B was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 80° C. The reaction was kept warm for 48 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0132] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 5% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 550 at a rate of 5°C / min, and the temperature was kept at this temperature for 4 hours for high-temperature calcination to obtain a primary sample 2.

[0133] (5) 7.5 mL of 1.5 mg / L chloroplatinic acid solution and 7.5 mL of 0.5 mg / L ruthenium acetate solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 90 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0134] Example 5

[0135] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0136] (1) The untreated iron foil was washed with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water three times, each time for 20 minutes (surface area 10 cm 2 );

[0137] (2) dissolving 0.340 g of manganese phosphate, 0.367 g of cobalt phosphate, 0.485 g of bismuth nitrate, 0.6 g of urea, and 0.186 g of ammonium fluoride in 40 mL of deionized water to obtain a mixed solution B;

[0138] (3) Mixed solution B was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 180° C. The reaction was kept warm for 10 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0139] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 15% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 400°C at a rate of 3°C / min, and the temperature was kept at this temperature for 5 hours for high-temperature calcination to obtain a primary sample 2.

[0140] (5) 7.5 mL of 2.5 mg / L silver nitrate solution and 7.5 mL of 4 mg / L osmium chloride solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 10 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0141] Example 6

[0142] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0143] (1) The untreated carbon nanotubes were washed with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water for 3 times, each time for 20 minutes (surface area 10 cm 2 );

[0144] (2) Dissolve 0.340 g of zinc chloride, 0.367 g of cobalt phosphate, 0.485 g of bismuth nitrate, 0.6 g of urea, and 0.186 g of ammonium fluoride in 40 mL of deionized water to obtain a mixed solution B;

[0145] (3) The mixed solution C was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 180° C. The reaction was kept warm for 6 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0146] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 15% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 600°C at a rate of 4°C / min, and the temperature was kept at this temperature for 3 hours for high-temperature calcination to obtain the primary sample 2.

[0147] (5) 7.5 mL of 1 mg / L silver nitrate solution and 7.5 mL of 3 mg / L osmium chloride solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 180 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0148] Example 7

[0149] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0150] (1) The untreated iron and copper sheets were rinsed with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water three times, each time for 20 minutes (surface area 9 cm 2 );

[0151] (2) dissolving 0.44 g of chromium acetate, 0.970 g of gallium nitrate, 0.453 g of zirconium acetate, 0.6 g of urea, and 0.186 g of ammonium fluoride in 40 mL of deionized water to obtain a mixed solution B;

[0152] (3) Mixed solution B was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 220° C. The reaction was kept warm for 18 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0153] 4) The primary sample 1 obtained in step (3) was placed in a tube furnace, a mixture of hydrogen and argon (hydrogen accounting for 20% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 600°C at a rate of 4°C / min, and the temperature was continued to be kept for 3 hours for high-temperature calcination to obtain a primary sample 2.

[0154] (5) 7.5 mL of 0.5 mg / L ammonium chloropalladate solution and 7.5 mL of 1.5 mg / L iridium acetate solution were mixed to obtain a noble metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 40 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored noble metal single atom / cluster heterojunction catalyst.

[0155] Example 8

[0156] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0157] (1) The untreated graphene blocks were rinsed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 20 minutes (surface area of ​​10 cm 2 );

[0158] (2) 0.654 g of zinc acetylacetonate, 0.879 g of nickel acetylacetonate, 1.137 g of cerium sulfate, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0159] (3) Mixed solution B was placed in a 50 mL reactor, and the nickel mesh (surface area of ​​10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 200° C. The reaction was kept warm for 12 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0160] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 15% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 400°C at a rate of 20°C / min, and the temperature was kept at this temperature for 6 hours for high-temperature calcination to obtain the primary sample 2.

[0161] (5) 7.5 mL of 3.5 mg / L silver nitrate solution and 7.5 mL of 1.5 mg / L osmium chloride solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 100 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0162] Example 9

[0163] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0164] (1) The untreated cobalt foil was rinsed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 30 minutes (surface area 10 cm 2 );

[0165] (2) 0.885 g of cobalt acetate, 0.750 g of zinc oxalate, 0.932 g of ytterbium sulfate, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0166] (3) Mixed solution B was placed in a 50 mL reactor, and the cobalt foil (surface area 10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 280° C. The reaction was kept warm for 6 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0167] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 50% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 300°C at a rate of 5°C / min, and the temperature was kept at this temperature for 2 hours for high-temperature calcination to obtain a primary sample 2.

[0168] (5) 7.5 mL of 1 mg / L ammonium chlororuthenate solution and 7.5 mL of 2 mg / L platinum acetate solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 100 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide anchored precious metal single atom / cluster heterojunction catalyst.

[0169] Example 10

[0170] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0171] (1) The untreated iron mesh was rinsed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 30 minutes (surface area 10 cm 2 );

[0172] (2) 1.760 g of manganese acetylacetonate, 0.648 g of neodymium nitrate, 1.246 g of erbium sulfate, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0173] (3) Mixed solution B was placed in a 50 mL reactor, and the cobalt foil (surface area 10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 80° C. The reaction was kept warm for 24 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0174] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixed gas of hydrogen and argon (hydrogen accounting for 30% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 500°C at a rate of 10°C / min, and the temperature was kept at this temperature for 5 hours for high-temperature calcination to obtain a primary sample 2.

[0175] (5) 7.5 mL of 3 mg / L gold nitrate solution and 7.5 mL of 4 mg / L rhodium acetate solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added thereto. The solution was placed in a vacuum barrel and vacuum immersed for 60 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0176] Example 11

[0177] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0178] (1) The untreated nickel-molybdenum wire was rinsed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 30 minutes (surface area 10 cm 2 );

[0179] (2) 0.856 g of titanium citrate, 0.632 g of chromium chloride, 0.970 g of germanium nitrate, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0180] (3) Mixed solution B was placed in a 50 mL reactor, and the cobalt foil (surface area 10 cm) treated in step (1) was added. 2) was subjected to a solvent thermal reaction at a temperature of 140° C. The reaction was kept warm for 10 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0181] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixed gas of hydrogen and argon (hydrogen accounting for 20% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 600°C at a rate of 5°C / min, and the temperature was kept at this temperature for 3 hours for high-temperature calcination to obtain a primary sample 2.

[0182] (5) 7.5 mL of 1 mg / L platinum chloride solution and 7.5 mL of 4 mg / L ruthenium trichloride hydrate solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 90 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide anchored precious metal single atom / cluster heterojunction catalyst.

[0183] Example 12

[0184] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0185] (1) The untreated carbon black tube was rinsed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 30 minutes (surface area 10 cm 2 );

[0186] (2) 0.929 g of ferric iodide, 1.055 g of zinc nitrate, 1.046 g of dysprosium nitrate, 0.6 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0187] (3) Mixed solution B was placed in a 50 mL reactor, and the cobalt foil (surface area 10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a temperature of 280° C. The reaction was kept warm for 6 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0188] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixed gas of hydrogen and argon (hydrogen accounting for 10% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 550 at a rate of 6°C / min, and the temperature was kept at this temperature for 4 hours for high-temperature calcination to obtain a primary sample 2.

[0189] (5) 7.5 mL of 0.5 mg / L ammonium chloroosmate solution and 7.5 mL of 2.5 mg / L iridium bromide solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 150 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0190] Example 13

[0191] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0192] (1) The untreated copper foil was rinsed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 30 minutes (surface area 10 cm 2 );

[0193] (2) 0.929 g of ferric iodide, 1.055 g of copper nitrate, 1.046 g of dysprosium nitrate, 0.945 g of urea, and 0.186 g of ammonium fluoride were dissolved in 40 mL of deionized water to obtain a mixed solution B;

[0194] (3) Mixed solution B was placed in a 50 mL reactor, and the cobalt foil (surface area 10 cm) treated in step (1) was added. 2 ) was subjected to a solvent thermal reaction at a hydrothermal reaction temperature of 100° C. The reaction was kept warm for 36 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0195] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 25% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 720 at a rate of 8°C / min, and the temperature was kept at this temperature for 1.5 hours for high-temperature calcination to obtain the primary sample 2.

[0196] (5) 7.5 mL of 2 mg / L rhodium trichloride hydrate solution and 7.5 mL of 2 mg / L iridium bromide solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 180 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide anchored precious metal single atom / cluster heterojunction catalyst.

[0197] Example 14

[0198] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0199] (1) The untreated nickel-chromium sheet was rinsed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 30 minutes (surface area 10 cm 2 );

[0200] (2) Dissolve 0.538 g of cobalt nitrate, 0.6 g of urea, and 0.186 g of ammonium fluoride in 40 mL of deionized water to obtain a mixed solution B;

[0201] (3) Mixed solution B was placed in a 50 mL reactor, and the cobalt foil (surface area 10 cm) treated in step (1) was added. 2 ) was subjected to solvent thermal reaction at a hydrothermal reaction temperature of 240° C. The reaction was kept warm for 6 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0202] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 35% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 800°C at a rate of 15°C / min, and the temperature was kept at this temperature for 6 hours for high-temperature calcination to obtain a primary sample 2.

[0203] (5) 7.5 mL of 3 mg / L silver bromide solution and 7.5 mL of 4 mg / L ammonium chloroosmate solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added thereto. The solution was placed in a vacuum barrel and vacuum immersed for 20 minutes, then taken out and vacuum dried for 12 hours to obtain a single substance / alloy-metal hydroxide-anchored precious metal single atom / cluster heterojunction catalyst.

[0204] Example 15

[0205] A single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst is prepared by the following method:

[0206] (1) The untreated graphene blocks were washed twice with anhydrous ethanol, 2.0 mol / L hydrochloric acid and deionized water, each time for 30 minutes (surface area of ​​10 cm 2 );

[0207] (2) Dissolve 1.5 g of nickel nitrate, 0.6 g of urea, and 0.186 g of ammonium fluoride in 40 mL of deionized water to obtain a mixed solution B;

[0208] (3) Mixed solution B was placed in a 50 mL reactor, and the cobalt foil (surface area 10 cm) treated in step (1) was added. 2) was subjected to solvent thermal reaction at a hydrothermal reaction temperature of 140° C. The reaction was kept warm for 8 hours. After natural cooling, the product obtained after the hydrothermal reaction was taken out, filtered, washed, and vacuum dried for 24 hours to obtain a primary sample 1.

[0209] (4) The primary sample 1 obtained in step (3) was placed in a tubular furnace, a mixture of hydrogen and argon (hydrogen accounting for 35% of the volume fraction of the mixed gas) was introduced, the temperature was raised to 700°C at a rate of 7°C / min, and the temperature was kept at this temperature for 3 hours for high-temperature calcination to obtain the primary sample 2.

[0210] (5) 7.5 mL of 0.5 mg / L platinum fluoride solution and 7.5 mL of 0.5 mg / L sodium tetrachloropalladate solution were mixed to obtain a precious metal salt solution C, and the primary sample 2 obtained in step 4 was added. The solution was placed in a vacuum barrel and vacuum immersed for 180 minutes, then taken out and vacuum dried for 12 hours to obtain the elemental / alloy-metal hydroxide anchored precious metal single atom / cluster heterojunction catalyst.

[0211] The element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalysts prepared in Examples 1-15 were subjected to HER and OER tests in 1.0 mol / L potassium hydroxide solution, and HZOR tests were conducted in 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate solution, respectively. The specific operations are as follows:

[0212] (1) The element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalysts prepared in Examples 1-15 were used as working electrodes, and electrochemical tests were performed using an electrochemical workstation.

[0213] (2) The test conditions are as follows: a carbon rod is used as a counter electrode, a mercury / mercuric oxide electrode is used as a reference electrode, and the catalysts prepared in Examples 1-15 are used as working electrodes, respectively, to form 15 sets of three-electrode test systems. Then, HER and OER tests are performed in a 1.0 mol / L potassium hydroxide solution, HzOR test is performed in a 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate solution, and UOR test is performed in a 1.0 mol / L potassium hydroxide and 0.5 mol / L urea solution. The results are shown in Tables 1, 2, 3, and 4.

[0214] Table 1 HER electrochemical performance in 1.0 mol / L potassium hydroxide solution

[0215]

[0216] Table 2 OER electrochemical performance in 1.0 mol / L potassium hydroxide solution

[0217]

[0218]

[0219] Table 3 Electrochemical performance of HzOR in 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate solutions

[0220]

[0221] Table 4 Electrochemical performance of UOR in 1.0 mol / L potassium hydroxide and 0.5 mol / L urea solutions

[0222]

[0223] As can be seen from Table 1, 1.0 mol / L potassium hydroxide was used as the electrolyte for detection. -2 At a current density of -500 mA cm, the potential of the single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention in the electrochemical hydrogen evolution reaction is as high as -17 mV in Example 1 and as low as -67 mV in Example 8; at a current density of -500 mA cm -2 Under the potential of , the potential of the catalyst prepared by the present invention in the electrochemical hydrogen evolution reaction is as high as -121mV in Example 1 and as low as -201mV in Example 8; at the same time, the minimum Tafel slope is 45.98mV dec in Example 1. -1 The maximum value is 90.64mV dec of Example 8 -1 The test performance in Table 1 indicates that the elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention exhibits excellent HER performance in a 1.0 mol / L potassium hydroxide solution. The above test data indicate that Example 1 is the best example of the present invention.

[0224] As can be seen from Table 2, 1.0 mol / L potassium hydroxide solution was used as the electrolyte for detection. -2 At a current density of 500 mA cm, the potential in the oxygen evolution reaction of the element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention is as low as 1.34 V in Example 1 and as high as 1.38 V in Example 6 or Example 8; at a current density of 500 mA cm -2 Under the potential of , the lowest potential in the electrochemical hydrogen evolution reaction of the catalyst prepared by the present invention is 1.60V in Example 1 and the highest is 1.72V in Example 8; at the same time, the minimum Tafel slope is 78.92mV dec in Example 1. -1 The maximum value is 98.52mV dec of Example 8 -1The performance test results in Table 2 indicate that the elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention exhibits excellent OER performance in a 1.0 mol / L potassium hydroxide solution. The above test data indicate that Example 1 is the best embodiment of the present invention.

[0225] As can be seen from Table 3, 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate solution were used as electrolytes for detection. -2 At a current density of 500 mA cm, the potential of the electrochemical hydrazine oxidation reaction of the element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention is as low as -32 mV in Example 1 and as high as 13 mV in Example 12; at a current density of 500 mA cm -2 Under the potential of , the lowest potential of the catalyst prepared by the present invention in the electrochemical hydrazine oxidation reaction is 52mV in Example 1 and the highest is 108mV in Example 12; at the same time, the minimum Tafel slope is 35.94mV dec in Example 1. -1 The maximum value is 84.63mV dec of Example 12 -1 The performance test results in Table 3 indicate that the elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention exhibits excellent HzOR performance in a 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate solution. The above test data indicate that Example 1 is the best embodiment of the present invention.

[0226] As can be seen from Table 4, 1.0 mol / L potassium hydroxide and 0.5 mol / L urea solution were used as electrolytes for detection. -2 At a current density of 500 mA cm, the potential of the electrochemical urea oxidation reaction of the element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention is as low as 1.34 V in Example 1 and as high as 1.38 V in Example 5 or Example 12; at a current density of 500 mA cm -2 At a current density of 1.50, the potential of the catalyst prepared by the present invention in the electrochemical urea oxidation reaction is as low as 1.43 V in Example 1 and as high as 1.58 V in Example 5; at the same time, the minimum Tafel slope is 41.53 mV dec in Example 1. -1 The maximum value is 75.62mV dec of Example 5 -1 The performance test results in Table 1 indicate that the elemental / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst prepared by the present invention exhibits excellent UOR performance in a 1.0 mol / L potassium hydroxide and 0.5 mol / L urea solution. The above test data indicate that Example 1 is the best example of the present invention.

[0227] The element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 20 wt.% commercial Pt / C catalyst were subjected to hydrogen evolution linear sweep voltammetry in 1.0 mol / L potassium hydroxide solution. The scanned curve data are shown in FIG. Figure 5 .

[0228] like Figure 5 The LSV curves shown clearly reveal the HER electrochemical performance of the catalyst. Combined with the test data analysis in Table 1, it can be seen that at the same current density, the lower the overpotential value, the better the HER performance of the catalyst. It is worth noting that in alkaline electrolyte, the overpotential value of -10mA cm -2 At a current density of 1.5 Å, the catalyst prepared in this example only needs to apply an overpotential similar to that of a commercial Pt / C catalyst. This key data comparison fully demonstrates that the HER catalytic performance of the catalyst prepared in this example is close to that of a commercial Pt / C catalyst.

[0229] The element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 20 wt.% commercial Pt / C catalyst were subjected to Tafel slope detection in 1.0 mol / L potassium hydroxide solution. The detection curve data are shown in FIG. Figure 6 .

[0230] The Tafel slope is calculated by converting the linear sweep voltammetry curve data through a formula, and its value directly reflects the kinetic characteristics of the electrocatalytic reaction. The Tafel slope is negatively correlated with the reaction rate: the smaller the slope value, the faster the reaction kinetics; conversely, it reveals that there is a large energy barrier in the kinetic process. Figure 6 As shown, in a 1.0 mol / L KOH electrolyte system, it is particularly noteworthy that the Tafel slope of the catalyst prepared in Example 1 is lower than that of the commercial Pt / C catalyst, indicating that the catalyst prepared in Example 1 has fast reaction kinetics.

[0231] The single substance / alloy-metal hydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 40 wt.% commercial RuO2 / C catalyst were subjected to oxygen evolution linear sweep voltammetry in 1.0 mol / L potassium hydroxide solution. The scanned curve data are shown in FIG. Figure 7 .

[0232] Figure 7 The linear sweep voltammetry curve of the catalyst in this example directly demonstrates the excellent electrochemical properties of the catalyst. According to the evaluation criteria recognized in the field of electrochemistry, under the same current density, the lower the overpotential, the higher the efficiency of the catalyst in driving the OER reaction. When the current density reaches 10 mA cm-2 The overpotential value of the catalyst in 1.0 mol / L KOH medium is at the same level as that of the commercial RuO2 / C catalyst, which fully proves that its OER catalytic performance is comparable to that of the benchmark material.

[0233] To further explore the nature of the catalytic reaction kinetics, we conducted Tafel slope analysis on the elemental / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 40 wt.% commercial RuO2 / C catalyst under the same test conditions. The curve data of the detection is shown in Figure 8 As a mathematically derived parameter of the LSV curve, the Tafel slope directly quantifies the kinetic rate characteristics of the electrode reaction. Figure 8 The data clearly show that the Tafel slope values ​​of the two catalysts are relatively close, which indicates that the catalyst of this example not only has an intrinsic OER activity comparable to that of commercial catalysts, but also has a kinetic control mechanism during the electrode reaction that is comparable to that of commercial catalysts.

[0234] The element / alloy-metal hydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 20 wt.% commercial Pt / C catalyst were subjected to linear sweep voltammetry detection of hydrazine oxidation in a test solution containing 1.0 mol / L potassium hydroxide and 0.5 mol / L hydrazine hydrate solution as electrolytes. The scanned curve data are shown in FIG. Figure 9 .

[0235] Figure 9 The LSV curve clearly reveals the electrochemical performance characteristics of the catalyst HzOR. According to the generally accepted evaluation criteria in the field of electrocatalysis, under constant current density conditions, the lower the overpotential, the more efficient the catalyst is in driving the HzOR reaction. Figure 9 As shown, when the current density reaches 10 mA cm -2 When the overpotential value required by the catalyst of Example 1 in alkaline medium is at a similar energy threshold as that of the commercial Pt / C catalyst, indicating that its HzOR catalytic performance has reached the same level as that of the benchmark catalyst.

[0236] To further explore the electrode reaction kinetics, we conducted Tafel slope analysis on the element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 20 wt.% commercial Pt / C catalyst under the same test conditions. The curve data of the detection is shown in Figure 10 As a mathematical derivative parameter of the LSV curve, the Tafel slope is obtained by linear fitting, and its value directly quantifies the kinetic rate of the electrocatalytic reaction. Figure 10It shows that the Tafel slopes of the two catalysts show certain differences: the catalyst in Example 1 exhibits a smaller slope value, which indicates that its electrode reaction process has faster kinetic characteristics.

[0237] To evaluate the UOR electrochemical performance of the catalyst, we conducted linear sweep voltammetry tests on the element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 40 wt.% commercial RuO2 / C catalyst in a 1.0 mol / L KOH solution containing 0.5 mol / L urea. The polarization curves are shown in Figure 2. Figure 11 According to the general evaluation standards in the field of electrocatalysis, at the same current density, the lower the potential, the more efficient the catalyst is in driving the UOR reaction. Figure 11 It shows that when the current density reaches 10 mA cm -2 When the potential value of the catalyst of this embodiment is close to that of commercial RuO2 / C, it is fully proved that the UOR catalytic performance of the catalyst prepared in Example 1 is comparable to that of the benchmark material.

[0238] To further reveal the electrode reaction kinetics mechanism, we conducted Tafel slope analysis on the element / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst prepared in Example 1 and 40wt.% commercial RuO2 / C catalyst under the same test conditions. The curve data of the detection is shown in Figure 12 As a mathematically derived parameter of the LSV curve, the Tafel slope is obtained by linear fitting, and its value directly quantifies the kinetic rate of the electrocatalytic reaction. Figure 12 The data clearly show that the Tafel slope values ​​of the two catalysts are highly similar, indicating that the catalyst of this example not only has the UOR intrinsic activity comparable to that of the commercial catalyst, but also has the same level of kinetic control mechanism during the electrode reaction.

[0239] In summary, it can be seen that the catalyst prepared in Example 1 has good HER, OER, HzOR and UOR catalytic performance in 1.0 mol / L potassium hydroxide, 1.0 mol / L potassium hydroxide + 0.5 mol / L hydrazine hydrate, and 1.0 mol / L potassium hydroxide + 0.5 mol / L urea electrolytes, respectively. HER: -17 mV @ -10 mA cm -2 , -52mV@-100mA cm -2 , -121mV@-500mA cm -2 OER: 1.34 V @ 10 mA cm -2 , 1.56V@100mA cm -2 , 1.60V@500mA cm -2 ;HzOR:-32mV@10mA cm-2 , -16mV@100mA cm -2 , 52mV@500mA cm -2 ;UOR: 1.34VmV@10mA cm -2 , 1.39V@100mA cm -2 , 1.43V@500mA cm -2 .

[0240] It should be specifically stated that the description of the various embodiments herein should not be construed as limiting the scope of the patent rights. Based on the core innovative ideas of the present invention, any technical personnel who make appropriate adjustments, improvements or modifications to the technical solutions of the embodiments, or implement structural equivalent replacements, process equivalent conversions, and other innovative practices through the contents of the specification and drawings, regardless of whether the above-mentioned embodiments are implemented in the form of direct application or equivalent conversion, or whether these technical solutions are extended to other related technical fields, shall be deemed to fall within the scope of patent protection of the present invention.

Claims

1. A method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst, comprising the following steps: 1) dissolving metal salt A, urea and ammonium fluoride in deionized water to obtain a mixed solution B; The metal salt A is one or more of the following: iron salt, nickel salt, copper salt, cobalt salt, zinc salt, titanium salt, chromium salt, manganese salt, calcium salt, vanadium salt, gallium salt, germanium salt, strontium salt, yttrium salt, zirconium salt, niobium salt, cadmium salt, indium salt, tin salt, antimony salt, hafnium salt, tantalum salt, tungsten salt, rhenium salt, thallium salt, lead salt, bismuth salt, lanthanum salt, cerium salt, praseodymium salt, neodymium salt, samarium salt, europium salt, gadolinium salt, terbium salt, dysprosium salt, holmium salt, erbium salt, ytterbium salt or thulium salt; The mass ratio of the metal salt A, urea and ammonium fluoride is 2.5-20:3-5:1; 2) adding the mixed solution B and the pretreated support into a reactor for hydrothermal reaction at a temperature of 80-280° C. for a reaction time of 6-48 hours. After the reaction is completed, the mixture is cooled to room temperature, the reaction solution in the reactor is removed and filtered, and the filter cake is washed and dried to obtain a preliminary sample 1; The ratio of the input mass of the metal salt A to the surface area of ​​the pretreated support is 54-370:1 mg / cm 2 ; 3) placing the preliminary sample 1 prepared in step 2) in a calcining furnace, introducing a mixture of hydrogen and argon, wherein the volume fraction of hydrogen in the mixture is 5-50%, heating the mixture to 300-800° C. at a heating rate of 3-20° C. / min, and calcining the mixture at high temperature for 1.5-6 hours to obtain a preliminary sample 2; 4) placing the preliminary sample 2 into a solution of the noble metal compound C and vacuum impregnating it for 10-180 minutes; after the impregnation, removing the sample and drying it to obtain a single substance / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst; The noble metal compound C is one or a mixture of two of the following: a silver compound, a gold compound, an iridium compound, a platinum compound, a rhodium compound, a ruthenium compound, an osmium compound or a palladium compound; When the noble metal compound C is a mixture of two noble metal compounds, the concentration ratio of the two metal salts in the noble metal compound C solution is 1:1-5.

2. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 1, wherein the carrier in step 1) is a metal carrier or a non-metallic carrier, and the metal carrier is one of the following: metal mesh, metal sheet, metal wire, metal foil, alloy mesh, alloy sheet, alloy wire.

3. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 2, characterized in that: The metal mesh is one of the following: nickel mesh, copper mesh, titanium mesh, cobalt mesh or iron mesh; The alloy mesh is a nickel-iron mesh or a nickel-molybdenum mesh; The metal sheet is one of the following: nickel sheet, cobalt sheet, copper sheet, iron sheet or titanium sheet; The alloy sheet is one of the following: nickel-cobalt sheet, nickel-copper sheet, iron-copper sheet, nickel-iron sheet, stainless steel sheet, nickel-molybdenum sheet or nickel-chromium sheet; The metal wire is one of the following: nickel wire, cobalt wire, copper wire, iron wire, aluminum wire or titanium wire; The alloy wire comprises one of the following: nickel-iron wire or nickel-molybdenum wire; The metal foil is one of the following: nickel foil, cobalt foil, copper foil, iron foil, zinc foil or titanium foil; The non-metallic carrier is one of the following: carbon black tubes, carbon nanotubes, carbon fiber sheets, activated carbon fibers, graphene blocks, porous carbon blocks, carbon cloth, carbon felt, glass fiber mesh, layered graphite or expanded perlite.

4. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 1, characterized in that: In the step 3), after the preliminary sample 1 is placed in a calcining furnace for calcination, if the metal salt A contains only one metal salt, the metal salt A is calcined to form a simple substance, and the formed simple substance is one of the following: Fe, Ni, Cu, Co, Zn, Ti, Cr, Mn, Ca, V, Ga, Ge, Sr, Y, Zr, Nb, Cd, In, Sn, Sb, Hf, Ta, W, Re, Tl, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm; if the metal salt A contains two or more metal salts, the metal salt A is calcined to form an alloy, and the formed simple substance alloy is one of the following or a mixture of two or more: FeNi, FeCo, FeZ n, FeTi, FeCr, FeMn, FeV, FeNb, FeCd, FeIn, FeSn, FeSb, FeHf, FeTa, FeW, FeRe, FeTl, FePb, FeBi, CuZn, CuNi, CuCo, CuTi, CuCr, CuMn, CuV, CuNb, CuCd, C uIn, CuSn, CuSb, CuHf, CuTa, CuW, CuRe, CuTl, CuPb, CuBi, CuGa, CuGe, CuY, CuZr, NiCo, NiZn, NiTi, NiCr, NiMn, NiV, NiNb, NiCd, NiIn, NiSn, NiSb, NiHf , NiTa, NiW, NiRe, NiTl, NiPb, NiBi, CoZn, CoTi, CoCr, CoMn, CoV, CoNb, CoCd, CoIn, CoSn, CoSb, CoHf, CoTa, CoW, CoRe, CoTl, CoPb, CoBi, ZnTi, ZnCr, Zn Mn, ZnV, ZnNb, ZnCd, ZnIn, ZnSn, ZnSb, ZnHf, ZnTa, ZnW, ZnRe, ZnTl, ZnPb, ZnBi, TiCr, TiMn, TiV, TiNb, TiCd, TiIn, TiSn, TiSb, TiHf, TiTa, TiW, TiRe, T iTl, TiPb, TiBi, CrMn, CrV, CrNb, CrCd, CrIn, CrSn, CrSb, CrHf, CrTa, CrW, CrRe, CrTl, CrPb, CrBi, MnV, MnNb, MnCd, MnIn, MnSn, MnSb, MnHf, MnTa, MnW, MnRe, MnTl, MnPb, MnBi, VNb, VCd, VIn, VSn, VSb, VHf, VTa, VW, VRe, VTl, VPb, VBi, NbCd, NbIn, NbSn, NbSb, NbHf, NbTa, NbW, NbRe, NbTl, NbPb, NbBi, CdIn,<h2 style=";text-align:left;direction:ltr">CdSn,CdSb,CdHf,CdTa,CdW,CdRe,CdTl,CdPb,CdBi,InSn,InSb,InHf,InTa,InW,InRe,InTl,InPb,InBi,SnSb,SnHf ,SnTa,SnW,SnRe,SnTl,SnPb,SnBi,SbHf,SbTa,SbW,SbRe, SbTl,SbPb,SbBi,HfTa,HfW,HfRe,HfTl,HfPb,HfBi,TaW,T aRe,TaTl,TaPb,TaBi,WRe,WTl,WPb,WBi,ReTl,RePb,ReBi ,TlPb,TlBi,PbBi,LaCe,LaNi,LaCo,LaCu,LaZn,CeNi,CeC o,CeCu,CeZn,FeNiCo,FeNiZn,FeCoZn,FeTiCr,FeCrMnV,C uNiZn,CuNiCo,CuZnTi,CuCrMn,NiCoZn,NiCoTi,NiZnCr。, 5. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 1 or 4, characterized in that: In the step 4), the formed single atom / cluster is one of the following: Ag, Au, Ir, Pt, Rh, Os, Ru, Pd, AgAu, AgIr, AgPt, AgRh, AgRu, AgOs, AgPd, AuIr, AuPt, AuRh, AuRu, AuOs, AuPd, IrPt, IrRh, IrRu, IrOs, IrPd, PtRh, PtRu, PtOs, PtPd, RhRu, RhOs, RhPd, RuOs, RuPd, OsPd.

6. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 1, characterized in that: The carrier pretreatment method is as follows: first, the untreated carrier material is immersed in anhydrous ethanol, a hydrochloric acid solution with a concentration of 2.0 mol / L, and deionized water in sequence for washing, and the process is repeated 2 to 3 times, with each washing lasting 20 to 30 minutes.

7. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 1, characterized in that: The metal iron salt in the metal salt A in step 1) is one of the following: ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous oxalate, ferric sulfate, ferric chloride, ferric nitrate, ferric phosphate, ammonium ferric citrate, ferrous acetate, ferrous carbonate, ferrous bromide, ferric iodide, ferric perchlorate, ferric thiocyanate, ferric stearate, ferric benzoate; The metal manganese salt in the metal salt A in step 1) is one of the following: manganese chloride, manganese sulfate, manganese nitrate, manganese carbonate, manganese acetate, manganese oxalate, manganese phosphate, manganese bromide, manganese iodide, manganese fluoride, manganese perchlorate, manganese citrate, manganous sulfate, manganous acetate, manganous oxalate, manganous hydrogen phosphate, manganese pyrophosphate, manganese metasilicate; The metal nickel salt in the metal salt A in step 1) is one of the following: nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, nickel oxalate, nickel carbonate, nickel phosphate, nickel potassium cyanide, nickel thiocyanate, nickel fluoride, nickel bromide, nickel iodide, nickel perchlorate, nickel sulfamate, nickel formate, nickel propionate, nickel acetylacetonate, nickel tartrate, nickel citrate, nickel stearate, nickel benzoate; The copper metal salt in the metal salt A in step 1) is one of the following: copper sulfate, copper nitrate, copper chloride, copper acetate, copper oxalate, copper carbonate, copper phosphate, cuprous cyanide, cuprous iodide, copper bromide, copper perchlorate, copper silicate, basic copper carbonate, copper stearate, copper benzoate, copper citrate, copper acetylacetonate, copper formate, copper thiocyanate; The metal cobalt salt in the metal salt A in step 1) is one of the following: cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt phosphate, cobalt bromide, cobalt iodide, cobalt sulfide, cobalt fluoride, cobalt perchlorate, cobalt citrate, cobalt stearate, cobalt laurate, cobalt benzoate, ammonium cobalt chloride, ammonium cobalt sulfate, ammonium cobalt nitrate, cobalt hydrogen phosphate, cobaltous acetate; The metal zinc salt in the metal salt A in step 1) is one of the following: zinc sulfate, zinc nitrate, zinc chloride, zinc carbonate, zinc phosphate, zinc bromide, zinc fluoride, zinc iodide, zinc perchlorate, zinc acetate, zinc oxalate, zinc citrate, zinc stearate, zinc benzoate, zinc formate, zinc thiocyanate, zinc ammonium sulfate, zinc acetylacetonate; The metal titanium salt in the metal salt A in step 1) is one of the following: titanium sulfate, titanium chloride, titanium nitrate, titanyl sulfate, potassium fluorotitanate, titanium oxalate, titanium phosphate, titanium acetate, titanium acetylacetonate, titanium formate, titanium citrate, titanium bromide, titanium iodide, titanium carbonate; The metal chromium salt in the metal salt A in step 1) is one of the following: chromium sulfate, chromium chloride, chromium nitrate, chromium acetate, chromium oxalate, chromium phosphate, chromium carbonate, chromium bromide, chromium iodide, chromium fluoride, chromium perchlorate, chromium acetylacetonate, chromium citrate, chromium stearate, chromium benzoate, chromium formate, chromous sulfate, chromous chloride, chromium thiocyanate; The metal manganese salt in the metal salt A in step 1) is one of the following: manganese sulfate, manganese nitrate, manganese chloride, manganese carbonate, manganese phosphate, manganese acetate, manganese oxalate, manganese fluoride, manganese bromide, manganese iodide, manganese perchlorate, manganese acetylacetonate, manganese citrate, manganese stearate, manganese benzoate, manganese formate, manganese thiocyanate, and ammonium manganese sulfate; The metal calcium salt in the metal salt A in step 1) is one of the following: calcium carbonate, calcium phosphate, calcium sulfate, calcium chloride, calcium fluoride, calcium bromide, and calcium iodide; The metal vanadium salt in the metal salt A in step 1) is one of the following: ammonium vanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadyl sulfate, vanadyl oxalate, vanadium tetrachloride, vanadium trichloride, sodium vanadate, potassium vanadate, vanadium pentachloride, vanadium sulfate, vanadium phosphate; The metal zinc salt in the metal salt A in step 1) is one of the following: zinc sulfate, zinc nitrate, zinc chloride, zinc carbonate, zinc phosphate, zinc bromide, zinc fluoride, zinc iodide, zinc perchlorate, zinc acetate, zinc oxalate, zinc citrate, zinc stearate, zinc benzoate, zinc formate, zinc thiocyanate, zinc silicate, zinc molybdate, zinc tungstate, zinc ammonium sulfate, zinc acetylacetonate; The metal gallium salt in the metal salt A in step 1) is one of the following: gallium sulfate, gallium nitrate, gallium chloride, gallium phosphate, gallium acetate, gallium oxalate, gallium bromide, gallium fluoride, gallium iodide, gallium perchlorate, and gallium citrate; The metal germanium salt in the metal salt A in step 1) is one of the following: germanium chloride, germanium sulfate, germanium nitrate, germanium fluoride, germanium bromide, germanium iodide, germanium acetate, germanium oxalate, germanium phosphate, and germanium thiocyanate; The metal strontium salt in the metal salt A in step 1) is one of the following: strontium sulfate, strontium nitrate, strontium chloride, strontium carbonate, strontium phosphate, strontium bromide, strontium fluoride, strontium iodide, strontium acetate, strontium oxalate, and strontium chromate; The metal yttrium salt in the metal salt A in step 1) is one of the following: yttrium sulfate, yttrium nitrate, yttrium chloride, yttrium phosphate, yttrium acetate, yttrium oxalate, yttrium fluoride, yttrium carbonate; The metal zirconium salt in the metal salt A in step 1) is one of the following: zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium phosphate, zirconium acetate, zirconium oxalate, zirconium fluoride, zirconium carbonate, zirconium oxychloride; The metal niobium salt in the metal salt A in step 1) is one of the following: niobium chloride, niobium sulfate, niobium nitrate, niobium oxalate, niobium phosphate, potassium fluoroniobate, and niobium acetate; The metal cadmium salt in the metal salt A in step 1) is one of the following: cadmium sulfate, cadmium nitrate, cadmium chloride, cadmium acetate, cadmium carbonate, cadmium phosphate, cadmium bromide, cadmium fluoride, cadmium iodide, cadmium thiocyanate; The metal indium salt in the metal salt A in step 1) is one of the following: indium sulfate, indium nitrate, indium chloride, indium phosphate, indium acetate, indium fluoride, indium bromide, indium iodide, indium oxalate, indium perchlorate; The metal tin salt in step 1) is one of the following: stannous chloride, stannous sulfate, stannous nitrate, stannous acetate, stannous chloride, stannous sulfate, stannous nitrate, stannous phosphate, stannous oxalate, stannous fluoride; The metal antimony salt in the metal salt A in step 1) is one of the following: antimony chloride, antimony sulfate, antimony nitrate, antimony fluoride, antimony bromide, antimony iodide, antimony acetate, and antimony phosphate; The metal hafnium salt in the metal salt A in step 1) is one of the following: hafnium chloride, hafnium sulfate, hafnium nitrate, hafnium phosphate, hafnium acetate, hafnium fluoride, hafnium oxalate, and hafnium oxychloride; The metal tantalum salt in the metal salt A in step 1) is one of the following: tantalum chloride, tantalum sulfate, tantalum nitrate, tantalum oxalate, tantalum phosphate, tantalum acetate, tantalum fluoride, tantalum oxychloride; The metal tungsten salt in the metal salt A in step 1) is one of the following: sodium tungstate, ammonium tungstate, tungsten chloride, tungsten sulfate, tungsten nitrate, tungsten fluoride, tungsten acetate; The metal rhenium salt in the metal salt A in step 1) is one of the following: potassium perrhenate, rhenium chloride, rhenium sulfate, rhenium nitrate, rhenium fluoride, rhenium bromide, rhenium acetate, and rhenium thiocyanate; The metal thallium salt in the metal salt A in step 1) is one of the following: thallium sulfate, thallium nitrate, thallium chloride, thallium acetate, thallium carbonate, thallium bromide, thallium iodide, thallium fluoride, thallium oxalate; The metal europium salt in the metal salt A in step 1) is one of the following: europium fluoride, europium nitrate; The metal bismuth salt in the metal salt A in step 1) is one of the following: bismuth nitrate, bismuth sulfate, bismuth chloride, bismuth citrate, bismuth oxalate, bismuth acetate, bismuth fluoride, bismuth iodide, bismuth subnitrate; The metal lanthanum salt in the metal salt A in step 1) is one of the following: lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthanum acetate, lanthanum phosphate, lanthanum oxalate, lanthanum fluoride, lanthanum carbonate, lanthanum citrate; The metal cerium salt in the metal salt A in step 1) is one of the following: cerium sulfate, cerium nitrate, cerium chloride, cerium acetate, cerium oxalate, cerium fluoride, cerium phosphate, cerium carbonate, cerium citrate; The metal praseodymium salt in the metal salt A in step 1) is one of the following: praseodymium nitrate, praseodymium sulfate, praseodymium chloride, praseodymium acetate, praseodymium fluoride, praseodymium oxalate, praseodymium phosphate, and praseodymium carbonate; The metal neodymium salt in the metal salt A in step 1) is one of the following: neodymium nitrate, neodymium sulfate, neodymium chloride, neodymium acetate, neodymium fluoride, neodymium oxalate, neodymium phosphate, and neodymium carbonate; The metal samarium salt in the metal salt A in step 1) is one of the following: samarium nitrate, samarium sulfate, samarium chloride, samarium acetate, samarium fluoride, samarium oxalate, samarium phosphate, and samarium carbonate; The metal europium salt in the metal salt A in step 1) is one of the following: europium nitrate, europium sulfate, europium chloride, europium acetate, europium fluoride, europium oxalate, europium phosphate, and europium carbonate; The metal gadolinium salt in the metal salt A in step 1) is one of the following: gadolinium nitrate, gadolinium sulfate, gadolinium chloride, gadolinium acetate, gadolinium fluoride, gadolinium oxalate, gadolinium phosphate, and gadolinium carbonate; The metal terbium salt in the metal salt A in step 1) is one of the following: terbium nitrate, terbium sulfate, terbium chloride, terbium acetate, terbium fluoride, terbium oxalate, terbium phosphate, or terbium carbonate; The metal dysprosium salt in the metal salt A in step 1) is one of the following: dysprosium nitrate, dysprosium sulfate, dysprosium chloride, dysprosium acetate, dysprosium fluoride, dysprosium oxalate, dysprosium phosphate, and dysprosium carbonate; The metal holmium salt in the metal salt A in step 1) is one of the following: holmium nitrate, holmium sulfate, holmium chloride, holmium acetate, holmium fluoride, holmium oxalate, holmium phosphate, and holmium carbonate; The metal erbium salt in the metal salt A in step 1) is one of the following: erbium nitrate, erbium sulfate, erbium chloride, erbium acetate, erbium fluoride, erbium oxalate, erbium phosphate, and erbium carbonate; The metal ytterbium salt in the metal salt A in step 1) is one of the following: ytterbium nitrate, ytterbium sulfate, ytterbium chloride, ytterbium acetate, ytterbium fluoride, ytterbium oxalate, ytterbium phosphate, and ytterbium carbonate; The metal thulium salt in the metal salt A in step 1) is one of the following: thulium nitrate, thulium sulfate, thulium chloride, thulium acetate, thulium fluoride, thulium oxalate, thulium phosphate, and thulium carbonate.

8. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 1, characterized in that: The silver compound of the noble metal compound C in step 3) is one of the following: silver nitrate, silver sulfate, silver chloride, silver fluoride, silver bromide, silver iodide, silver acetate, silver carbonate, silver phosphate, silver oxalate, silver citrate, silver thiocyanate, silver cyanide, and silver perchlorate; The gold compound in the precious metal compound C in step 3) is one or two of the following: gold trichloride, potassium aurous cyanide, sodium gold thiosulfate, gold nitrate, gold sulfate, gold acetate, gold bromide, gold fluoride, gold iodide, and gold thiocyanate; The iridium compound in the noble metal compound C in step 3) is one of the following: iridium chloride, iridium nitrate, iridium sulfate, iridium fluoride, iridium bromide, iridium acetate, iridium oxalate, chloroiridic acid, ammonium hexachloroiridate, iridium thiocyanate; The platinum compound in the precious metal compound C in step 3) is one of the following: chloroplatinic acid, potassium chloroplatinite, platinum nitrate, platinum sulfate, platinum chloride, platinum fluoride, platinum bromide, platinum acetate, platinum oxalate, platinum cyanide, ammonium hexachloroplatinate; The rhodium compound in the precious metal compound C in step 3) is one of the following: rhodium chloride, rhodium nitrate, rhodium sulfate, rhodium fluoride, rhodium bromide, rhodium acetate, rhodium oxalate, ammonium chlororhodiumate, rhodium trichloride hydrate, rhodium thiocyanate; The ruthenium compound in the precious metal compound C in step 3) is one of the following: ruthenium chloride, ruthenium nitrate, ruthenium sulfate, ruthenium fluoride, ruthenium bromide, ruthenium acetate, ruthenium oxalate, ammonium chlororuthenate, ruthenium trichloride hydrate, ruthenium thiocyanate; The osmium compound in the noble metal compound C in step 3) is one of the following: osmium chloride, osmium nitrate, osmium sulfate, osmium fluoride, osmium bromide, osmium acetate, osmium oxalate, ammonium chloroosmate, and osmium thiocyanate. The palladium compound in the noble metal compound C in step 3) is one of the following: palladium chloride, palladium nitrate, palladium sulfate, palladium fluoride, palladium bromide, palladium acetate, palladium oxalate, palladium cyanide, ammonium chloropalladate, and sodium tetrachloropalladate.

9. The method for preparing a single substance / alloy-metal oxyhydroxide anchored noble metal single atom / cluster heterojunction catalyst according to claim 1, characterized in that: In the step 4), the concentration of the noble metal compound C solution is 0.5-4 mg / L.

10. A single substance / alloy-metal oxyhydroxide-anchored noble metal single atom / cluster heterojunction catalyst, characterized by: The compound is prepared by the preparation method according to any one of claims 1 to 9.

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