Metal-doped ruthenium oxide nanomaterial, method for producing the same, and use thereof

Abstract

The present invention belongs to the technical field of advanced inorganic nanomaterials, and specifically relates to metal-doped ruthenium oxide nanomaterials, a method for manufacturing the same, and their use. The metal-doped ruthenium oxide nanomaterials are acid-insoluble metal oxide-doped ruthenium oxide nanomaterials or transition metal-doped ruthenium oxide nanomaterials. The molecular formula of the acid-insoluble metal-doped ruthenium oxide nanomaterials is M x Ru 1-x O 2 where M is an acid-insoluble metal, and the acid-insoluble metal is one or more selected from niobium, titanium, zirconium, hafnium, tungsten, molybdenum, and tantalum. Alternatively, the molecular formula of the transition metal-doped ruthenium oxide nanomaterials is M x Ru 1-x O 2 where M is a transition metal, and the transition metal is one selected from Cr, Mn, Ge, In, Sn, Sb, Nb, Ti, Zr, Hf, W, Mo, Ta, and Pt. In the present invention, by highly and uniformly dispersing the metal in the ruthenium oxide material, ruthenium, which is the active site, is well adjusted and controlled, and the material stability and activity in the oxygen evolution reaction are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of advanced inorganic nanomaterials, and specifically relates to metal-doped ruthenium oxide nanomaterials, a method for manufacturing the same, and their use.

Background Art

[0002] With the consumption of conventional fossil energy and the worsening of environmental pollution problems caused by its combustion, carbon dioxide emissions are increasing, and the goals of "carbon peak out" and "carbon neutral" still face severe challenges. Therefore, the development of new sustainable clean energy sources to replace fossil fuels has become an urgent task. Currently, solar energy, wind energy, bioenergy, tidal energy, and hydrogen energy are relatively mature new alternative energy sources. Among them, hydrogen energy has attracted attention as a clean energy source with high energy density, cleanliness, and no pollution. In addition, there are many hydrogen energy sources, such as hydrogen production from fossil fuels, hydrogen production by carbon capture, and hydrogen production by water electrolysis. Among the numerous production processes, hydrogen production by water electrolysis has a relatively simple process and relatively mature technology. Hydrogen production by water electrolysis can be divided into alkaline water electrolysis hydrogen production technology (ALK), solid oxide electrolysis cell hydrogen production technology (SOEC), and proton exchange membrane water electrolysis technology (PEM). Compared with ALK technology, PEM hydrogen production has a high operating current density (exceeding 1 A / cm 2 ), high overall efficiency (74% - 87%), high hydrogen volume fraction (>99.99%), high gas generation pressure (3 - 4 MPa), fast dynamic response speed, and can also cope with the fluctuations of renewable energy power generation. Therefore, it is considered the most promising water electrolysis hydrogen production technology for development.

[0003] However, due to the local superacidity and oxidizing properties of the anode of PEM electrolyzers, common transition metal catalysts such as iron, cobalt, and nickel dissolve rapidly and it is difficult to function stably. Iridium oxide is currently the catalyst commercially used for PEM because of its extremely high stability in acidic oxygen evolution. However, its price is soaring, and due to the scarcity of resources, it is becoming difficult to utilize it on a large scale to meet future hydrogen energy demands. With the successful production of domestic proton exchange membranes, in the future, the cost of the membrane will be significantly reduced, and finding an alternative acidic oxygen evolution catalyst with good activity and stability will be the key to reducing the cost of pure water electrolysis.

[0004] The acidic oxygen evolution activity of ruthenium oxide is very high, but the potential of 1.33 V (compared with the standard hydrogen electrode) when RuO 4 is oxidized is within the operating potential of the oxygen evolution reaction. Therefore, the oxidation of ruthenium is involved in the oxygen evolution process, resulting in the formation of expensive ruthenium oxide, which dissolves in the electrolyte and ultimately leads to the loss of active sites and the degradation of the catalytic properties of the oxygen evolution reaction. However, due to its low price, designing a ruthenium-based oxygen evolution catalyst with high activity and stability is very promising but difficult.

[0005] In recent years, scientific researchers have made great efforts to improve the oxygen evolution activity and stability of ruthenium-based catalysts. For example, by doping transition metals such as iron, cobalt, nickel, and chromium into ruthenium oxide, defects are introduced into ruthenium oxide, the morphology of ruthenium oxide is adjusted and controlled, or ruthenium oxide is supported on a stable substrate. Ultimately, the electronic structure of ruthenium oxide changes, the adsorption to oxygen-containing intermediates is improved, and the electrode catalytic properties and stability of oxygen evolution are further enhanced. The problems of low activity and poor stability have not yet been solved.

[0006] To solve the above problems, the present invention is proposed.

Summary of the Invention

Problems to be Solved by the Invention

[0007] In the present invention, a metal oxide-doped ruthenium oxide nanoparticle that is highly active and stable when used as an acidic oxygen generation electrode material is produced using a sol-gel method, a solvothermal method, and a ball milling method.

Means for Solving the Problems

[0008] A first aspect of the present invention discloses a metal oxide-doped ruthenium oxide nanoparticle having a molecular formula of M x Ru 1-x O 2 , where M is a poorly acid-soluble metal, and the poorly acid-soluble metal is one or more selected from niobium, titanium, zirconium, hafnium, tungsten, molybdenum, and tantalum.

[0009] For example, the poorly acid-soluble metal is one, two, three, four, five, six, or seven selected from niobium, titanium, zirconium, hafnium, tungsten, molybdenum, and tantalum.

[0010] In this specification, the poorly acid-soluble metal is defined as a metal oxide having a solubility of less than 10 -5 in dilute inorganic acid (10% - 20% inorganic acid) at room temperature.

[0011] Preferably, in the metal oxide-doped ruthenium oxide nanoparticle, the poorly acid-soluble metal is doped inside the lattice of ruthenium oxide and replaces a part of the position of ruthenium in the lattice. Further, the poorly acid-soluble metal is uniformly dispersed inside the ruthenium oxide crystal.

[0012] Preferably, the size of the nanoparticles is 5 - 2000 nm, more preferably 50 - 200 nm.

[0013] Preferably, the metal oxide-doped ruthenium oxide nanoparticle has a rough and porous surface.

[0014] Preferably, in the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, the acid-insoluble metal and ruthenium are uniformly dispersed.

[0015] Preferably, in the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, the doping rate of the acid-insoluble metal is 1% to 50% based on the total molar fraction of the metals in the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial. The calculation formula for the doping rate of the acid-insoluble metal is Nacid-insoluble metal / (Nacid-insoluble metal + Nruthenium), where N is the molar amount.

[0016] Preferably, in the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, ruthenium oxide has (101) and (110) crystal planes. The interplanar spacing of the (101) crystal plane is 0.256 nm, and the interplanar spacing of the (110) crystal plane is 0.316 nm or 0.317 nm.

[0017] In ordinary ruthenium oxide, the interplanar spacing of the (101) crystal plane is 0.254 nm, and the interplanar spacing of the (110) crystal plane is 0.315 nm.

[0018] Judging from the lattice spacing, the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial of the present invention has a slightly wider lattice spacing than that of the ordinary ruthenium oxide material.

[0019] The second aspect of the present invention is Putting a ligand into a solution containing an acid-insoluble metal source and a ruthenium source to obtain a mixture, mixing the above mixture at a constant temperature in a sealed container for several hours, then opening the lid of the container, and evaporating the solvent by, for example, evaporation to dryness or freeze-drying, scraping the powder to obtain a metal complex precursor (step (1)); Putting the metal complex precursor obtained in step (1) into a muffle furnace, heating it to a desired temperature and keeping it warm for several hours, naturally cooling and taking it out, and obtaining the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a powder (step (2)). A method for producing the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial according to the first aspect, which is a sol-gel method, is provided.

[0020] Preferably, the acid-insoluble metal source is one or more selected from metal chlorides of acid-insoluble metals, organoesterified products of acid-insoluble metals, carbonyl compounds of acid-insoluble metals, oxalates of acid-insoluble metals, and ammonium oxalates of acid-insoluble metals, The ruthenium source is one or more of ruthenium chloride, ruthenium carbonyl, acetylacetonato ruthenium, or ruthenium(III) nitrosyl nitrate, The ligand is a polymer containing a plurality of coordination sites.

[0021] More preferably, the polymer containing the plurality of coordination sites is one or more selected from polyvinyl alcohol, polyethylene glycol, polyethylene diamine, polylactic acid, polyvinyl pyrrolidone, polypyridine, polypyrrole, and polyamide.

[0022] The solution containing the acid-insoluble metal source and the ruthenium source may be an aqueous solution or an alcohol solution, as long as the acid-insoluble metal source and the ruthenium source can be dissolved.

[0023] Preferably, in the mixture of step (1), the concentration of the acid-insoluble metal source is 0.01 to 1 mol / L, the concentration of the ruthenium source is 0.1 to 1 mol / L, and the concentration of the complex is 1 to 40 g / L.

[0024] Preferably, in step (1), the temperature for mixing while sealing at a constant temperature is 70 to 150 °C, and the time is 10 to 15 h.

[0025] Preferably, in step (2), the rate of temperature increase is 1 to 10 °C / min, the desired temperature is 400 to 600 °C, and the heat preservation time is 3 to 6 hours.

[0026] The third aspect of the present invention is Put a solution of an acid-insoluble metal source and a ruthenium source into a hydrothermal treatment kettle, perform ultrasonic treatment until all are dissolved, add an alkali source to obtain a reaction solution, put the hydrothermal treatment kettle into a constant-temperature oven at 100 - 200 °C, keep warm for 8 - 16 hours, take out the hydrothermal treatment kettle, naturally cool it to room temperature, then take out the precipitate generated by the reaction, wash it and bake it to obtain a powder, which is step A; Put the powder baked in step A above into a boat, put the boat into a muffle furnace, set the heating rate to 5 - 10 °C / min, heat it up to 400 - 600 °C, keep warm for 2 - 8 h, then naturally cool it to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a black powder sample, which is step B, and it includes; In step A, in the reaction solution, the concentration of the acid-insoluble metal source is 0.001 - 1 mol / L, the concentration of the ruthenium source is 0.1 - 1 mol / L, and the concentration of the alkali source is 0.5 - 4 mol / L. A method for manufacturing an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial according to the solvothermal method described in the first aspect is provided.

[0027] The acid-insoluble metal source is one or more selected from acid-insoluble metal chlorides, acid-insoluble metal organic esterified compounds, acid-insoluble metal carbonyl compounds, acid-insoluble metal oxalates, and ammonium oxalates of rare acid-insoluble metals; The ruthenium source is one or more of ruthenium chloride, acetylacetonato ruthenium, ruthenium carbonyl, or ruthenium(III) nitrosyl nitrate.

[0028] The alkali source is one or more of urea and aqueous ammonia.

[0029] In step A, the solution of the acid-insoluble metal source and the ruthenium source is an aqueous solution or an alcohol solution, as long as the acid-insoluble metal source and the ruthenium source can be dissolved.

[0030] The fourth aspect of the present invention is Put ruthenium oxide and an oxide of an acid-insoluble metal into a ball milling tank, perform ball milling 2 to 3 times for 3 to 6 hours each time to obtain a precursor powder. Put the precursor powder into a boat, put the boat into a muffle furnace, set the heating rate at 5 to 10 °C / min, heat it up to 400 to 800 °C, keep it warm for 6 to 12 h, then cool it naturally to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a black powder sample. The molar ratio of the ruthenium oxide to the oxide of the acid-insoluble metal is 99:1 to 1:1, and it is a ball milling method. Provided is a method for producing an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial according to the first aspect.

[0031] A fifth aspect of the present invention provides the use of the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial according to any one of the first aspects as an electrode material.

[0032] Preferably, it is the use as an oxygen evolution anode material in the acidic electrolysis of water of the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial.

[0033] In the present invention, when the transition metal-doped ruthenium oxide nanomaterial produced by the hydrothermal treatment method is used as an acidic oxygen evolution electrode material, it has high activity and excellent stability.

[0034] A sixth aspect of the present invention discloses a transition metal-doped ruthenium oxide nanomaterial having a molecular formula of M x Ru 1-x O 2 wherein M is a transition metal, and the transition metal is one selected from Cr, Mn, Ge, In, Sn, Sb, Nb, Ti, Zr, Hf, W, Mo, Ta, Pt.

[0035] Preferably, in the transition metal-doped ruthenium oxide nanomaterial, the transition metal is doped inside the ruthenium oxide crystal to replace a part of the position of ruthenium in the lattice, and the transition metal is uniformly dispersed inside the ruthenium oxide crystal.

[0036] Preferably, the size of the nanoparticles is 5 to 2000 nm.

[0037] Preferably, the transition metal-doped ruthenium oxide nanomaterial has rough-surfaced nanoparticles.

[0038] Preferably, in the transition metal-doped ruthenium oxide nanomaterial, the transition metal and ruthenium are uniformly dispersed.

[0039] Preferably, in the transition metal-doped ruthenium oxide nanomaterial, the transition metal doping rate is 1% to 50% based on the total molar fraction of the metal in the transition metal-doped ruthenium oxide nanomaterial. The calculation formula for the transition metal doping rate is Ntransition metal / (Ntransition metal + Nruthenium), where N is the molar fraction.

[0040] The seventh aspect of the present invention is Putting a soluble transition metal source into a solution containing a soluble ruthenium source in sequence to obtain a mixture, stirring the above mixture sufficiently, adding a polymer containing a plurality of coordination sites, further stirring sufficiently, transferring the mixture to a hydrothermal treatment kettle, keeping it warm in a constant temperature oven for several hours, then taking it out, naturally cooling to room temperature, washing, centrifuging, and drying to obtain a precursor containing a transition metal in step (1); A hydrothermal treatment method including step (2) of putting the transition metal precursor obtained in step (1) into a muffle furnace, raising the temperature to a desired temperature, keeping it warm for several hours, naturally cooling, and then taking it out to obtain the transition metal-doped ruthenium oxide nanomaterial as a powder. Preferably, the transition metal source is one or more of transition metal chlorides, transition metal expensive compounds, transition metal organic esterified products, transition metal carbonyl compounds, and transition metal oxalates. The ruthenium source is one or more of ruthenium chloride, acetylacetonato ruthenium, ruthenium carbonyl, or ruthenium(III) nitrosyl nitrate. The polymer containing the plurality of ligand sites is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylene diamine, polylactic acid, polypyridine, and polyamide, and provides a method for producing the transition metal-doped ruthenium oxide nanomaterial according to the sixth aspect.

[0041] The solution containing the transition metal source and the ruthenium source is an aqueous solution or an alcohol solution, thereby dissolving the transition metal source and the ruthenium source.

[0042] Preferably, the soluble chromium source is potassium dichromate and chromium chloride.

[0043] Preferably, the soluble manganese source is potassium permanganate and manganese chloride tetrahydrate.

[0044] Preferably, the soluble germanium source is germanium chloride.

[0045] Preferably, the soluble indium source is indium chloride.

[0046] Preferably, the soluble tin source is tin tetrachloride pentahydrate.

[0047] Preferably, the soluble antimony source is antimony chloride.

[0048] Preferably, the soluble niobium source is one of niobium chloride, niobium oxalate, and niobium pentoxide.

[0049] Preferably, the soluble titanium source is titanium chloride.

[0050] Preferably, the soluble zirconium source is zirconium chloride.

[0051] Preferably, the soluble hafnium source is hafnium oxide.

[0052] Preferably, the soluble tungsten source is tungsten oxide.

[0053] Preferably, the soluble molybdenum source is molybdenum chloride.

[0054] Preferably, the soluble tantalum source is tantalum chloride.

[0055] Preferably, the soluble platinum source is chloroplatinic acid.

[0056] Preferably, in the mixture of step (1), the concentration of the transition metal source is 0.001 - 1 mol / L, the concentration of the ruthenium source is 0.1 - 1 mol / L, and the concentration of the polymer is 1 - 50 g / L.

[0057] Preferably, in step (1), the temperature of the constant temperature oven is 100 - 180 °C and the time is 4 - 10 h.

[0058] Preferably, in step (2), the heating rate is 1 - 10 °C / min, the desired temperature is 300 - 500 °C, and the heat preservation time is 3 - 5 h.

[0059] The eighth aspect of the present invention provides the use of the transition metal-doped ruthenium oxide nanomaterial according to any one of the sixth aspects as an electrode material.

[0060] Preferably, the transition metal-doped ruthenium oxide nanomaterial is used as an oxygen evolution anode material in the acidic electrolysis of water.

[0061] Preferably, the transition metal-doped ruthenium oxide nanomaterial improves the activity and stability of the material towards the water electrolysis reaction.

[0062] The above technical solutions may be freely combined if there is no contradiction.

[0063] Compared with the prior art, the present invention has the following beneficial effects.

[0064] The acid-insoluble metal oxide-doped ruthenium oxide nanomaterial of the present invention has the following advantages.

[0065] (1) The acid-insoluble metal oxide-doped ruthenium oxide nanomaterial of the present invention is reported for the first time as an acid-insoluble metal doped into the interior of ruthenium oxide crystals to replace part of the position of ruthenium oxide in the lattice. The acid-insoluble metal doping does not destroy the inherent structure of ruthenium oxide and completely maintains the crystal structure of rutile-phase ruthenium oxide. In addition, the acid-insoluble metal is highly uniformly dispersed in the material, and no heterogeneous phase of the oxide of the acid-insoluble metal is generated. Therefore, ruthenium at the active site is sufficiently adjusted and controlled and maintains a stable state during the oxygen evolution reaction.

[0066] (2) The acid-insoluble metal oxide-doped ruthenium oxide nanomaterial of the present invention has uniform particle size, is porous, and has a simple synthesis method. The acid-insoluble metal oxide-doped ruthenium oxide nanomaterial further reduces the usage amount of precious metal ruthenium. Due to the doping of the acid-insoluble metal, the covalent bond between ruthenium and oxygen is weakened by the introduction of the acid-insoluble metal, and ruthenium at the active site becomes a lower valence number. When the obtained acid-insoluble metal-doped ruthenium oxide is used as an oxygen evolution anode material in the acidic electrolysis of water, it has high activity and stability. In particular, in the material of the present invention, the advantages of the acid-insoluble metal element are as follows. 1. It does not dissolve in the acidic electrolyte and maintains the stability of the material. 2. The introduction of the acid-insoluble metal element weakens the covalent bond between ruthenium and oxygen. The reasons are as follows: (1) The acid-insoluble metal element and its oxide have high acid stability and antioxidant properties, can stably adjust and control the active site during oxygen evolution, and can improve the stability of ruthenium oxide. (2) According to the adsorption theory, since the acid-insoluble metal has weak adsorption to the oxygen-containing intermediate, when doped into the lattice of ruthenium oxide, it improves the adsorption of the oxygen-containing intermediate by the ruthenium site, ultimately leading to an improvement in the activity of the ruthenium site. On the other hand, existing elements of iron, cobalt, nickel, and chromium, which are often doped with ruthenium oxide, do not have the above effects. Doping of iron, cobalt, nickel, and chromium usually does not conform to tetravalent ruthenium oxide due to its low valence, resulting in oxygen defects. Eventually, the oxygen generation reaction mechanism changes to a lattice oxygen oxidation mechanism. As a result, the oxygen generation reaction activity is improved, but due to the instability of the oxygen defects, the stability of the catalyst cannot be maintained.

[0067] (3) Regarding the activity, when the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial of the present invention is used as an oxygen generation anode material in the acidic electrolysis of water, the specific activity is high when the doping amount of the acid-insoluble metal is 1 at% to 50 at% (at% is the total molar fraction of the metal based on the total molar mass of the metal in the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial). Specifically, from FIG. 7, the acid-insoluble metal oxide-doped ruthenium oxide nanomaterials obtained in Example 1 and Example 2 have good oxygen generation characteristics in water electrolysis, and the overpotentials are 196 mV and 219 mV at a current density of 10 mA / cm 2 which are lower than the overpotential of 320 mV of commercially available ruthenium dioxide.

[0068] (4) Regarding the stability, when the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial of the present invention is used as an oxygen generation anode material in the acidic electrolysis of water, the constant current polarization curve can be stably maintained for 360 h even under the operating conditions of a high current density of 100 and 200 mA cm -2 . From this, it was confirmed that the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial is excellent in the stability of the acidic oxygen generation reaction.

[0069] (5) The manufacturing method of the present invention has three methods: the sol-gel method, the solvothermal method, and the ball milling method. The sol-gel method is to perform synthesis by combining a simple sol-gel reaction and air calcination conditions. This method is simple, low-cost, has good reproducibility, is environmentally friendly, enables scale-up of production, and is suitable for industrialization. The manufacturing method described in the present invention is simple and provides a new idea for synthesizing a highly active electrode material.

[0070] (6) In particular, in the sol-gel method of the present invention, a multidentate ligand polymer is used to form a complex with metal cations. The multidentate ligand of the polymer helps to uniformly disperse multiple metals in the final product compared to low-molecular complexes, and can improve the activity and stability of the material.

[0071] (7) In the solvothermal method of the present invention, since it is necessary to use a weak alkali source such as urea or aqueous ammonia as the alkali source, it is possible to reduce the slow release of hydroxide ions by the weak alkali source at high temperature, thereby slowly coprecipitating ruthenium and acid-insoluble metal ions and preventing the separation of metal phases caused by excessive changes in the pH value in the hydrothermal process.

[0072] The transition metal-doped ruthenium oxide nanomaterial of the present invention has the following advantages.

[0073] (1) In the transition metal-doped ruthenium oxide nanomaterial of the present invention, the transition metal is doped inside the ruthenium oxide crystal, replacing a part of the positions of ruthenium oxide in the lattice without destroying the inherent structure of ruthenium oxide, that is, completely maintaining the crystal structure of the rutile-phase ruthenium oxide. In addition, the transition metal is highly uniformly dispersed in the material, and no oxide impurity phase is generated. Therefore, ruthenium at the active site is sufficiently adjusted and controlled, and maintains a stable state during the oxygen evolution reaction.

[0074] (2) The transition metal-doped ruthenium oxide nanomaterial of the present invention has uniform particle sizes and a simple synthesis method. The transition metal-doped ruthenium oxide nanomaterial further reduces the usage amount of precious metal ruthenium. After the transition metal is doped, the introduction of the transition metal weakens the covalent bond of Ru-O, and ruthenium at the active site becomes a lower valence number. When the transition metal-doped ruthenium oxide nanomaterial is used as an oxygen evolution anode material in the acidic electrolysis of water, it has high activity and stability. In particular, in the material of the present invention, the advantages of the transition metal element are as follows. 1. During the stability test of the acidic electrolyte, the catalyst does not dissolve, and its constant current polarization curve can be stably maintained for a long time even under the operating conditions of high current density. 2. The introduction of transition metals such as manganese, chromium, and tin weakens the covalent bond of the Ru-O bond. The reasons are as follows: (1) Regarding stability, for transition metal elements such as manganese, chromium, and tin, these transition metals exist in a high-temperature and high-pressure liquid during production, or their most expensive compounds are used as transition metal sources, so they are in a fully oxidized liquid environment, and their oxides all have strong acid stability. Therefore, they play a role in stably adjusting and controlling the ruthenium active site during the acidic oxygen evolution process, improving the stability of ruthenium oxide. (2) Regarding activity, by doping transition metals such as manganese, chromium, and tin into ruthenium oxide, the center of the d band of the ruthenium active site is adjusted, the state of the back-bonding surface adsorbate decreases, the free energy of the rate-determining step decreases, and finally the intrinsic activity of ruthenium oxide is improved. Transition metals with low valences and low acid stability such as iron, cobalt, and nickel do not have the above effects. This is usually because their low valences do not match tetravalent ruthenium oxide, causing oxygen defects and finally changing the oxygen generation reaction mechanism to a lattice oxygen oxidation mechanism. Although it improves the activity of the catalyst in the acidic oxygen generation reaction, the stability of the catalyst cannot be maintained due to oxygen defects.

[0075] (3) When the transition metal-doped ruthenium oxide nanomaterial of the present invention is used as an oxygen evolution anode material in the acidic electrolysis of water, when the doping amount of the transition metal is 1 at% to 50 at% (at% is the metal molar fraction based on the total molar fraction of the metal in the transition metal-doped ruthenium oxide nanomaterial), the intrinsic activity is very high. Specifically, from FIGS. 10, 18, 25, 32, and 33, the transition metal-doped ruthenium oxide nanomaterials obtained in Examples 1 to 18 have good oxygen evolution characteristics in water electrolysis, and the overvoltage at a current density of 10 mA / cm 2 is lower than the overvoltage of 320 mV of commercially available ruthenium dioxide.

[0076] (4) When the transition metal-doped ruthenium oxide nanomaterial of the present invention is used as an oxygen evolution anode material in the acidic electrolysis of water, even under the operating conditions of a high current density of 200 mA cm -2 , the constant current polarization curve can be stably maintained for 80 to 100 h. From this, it was confirmed that the transition metal-doped ruthenium oxide nanomaterial is excellent in the stability of the acidic oxygen evolution reaction.

[0077] (5) The production method of the present invention is a hydrothermal method. The hydrothermal method is to perform synthesis by combining a simple reaction in a sealed reactor and air calcination conditions. This method is simple, low-cost, has good reproducibility, the obtained powder has high purity, good dispersibility, is useful for environmental purification, and the production scale-up is also possible. The production method described in the present invention provides a new idea for synthesizing a highly active electrode material.

[0078] (6) In particular, in the hydrothermal method of the present invention, a polymer having a multidentate ligand is used to form a complex with a metal cation. When a polymer having a multidentate ligand is added, the possibility of aggregation of fine particles is avoided, and it contributes to the uniform dispersion of transition metals such as doped manganese, chromium, and tin in the rutile lattice of ruthenium oxide, thereby improving the activity and stability of the material.

Brief Description of the Drawings

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Embodiments for Carrying out the Invention

[0080] Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. For experimental methods where specific conditions are not specified in the examples, they usually follow the conventional conditions and the conditions described in the manual, or the conditions recommended by the manufacturer. General apparatuses, materials, reagents, etc. are available as commercially available products unless otherwise specified. All raw materials required in the following examples and comparative examples are commercially available.

[0081] In the following experiments, a three - electrode system was used to test the oxygen evolution activity of the acid - insoluble metal oxide - doped ruthenium oxide nanomaterial of the present invention in water electrolysis and obtain a polarization curve. In the three - electrode system, a silver / silver chloride electrode was used as the reference electrode, a platinum sheet electrode was used as the counter electrode, and the acid - insoluble metal oxide - doped ruthenium oxide nanomaterial obtained in this example was used as the working electrode. When it is necessary to make a comparison, the following specific other materials are used as the working electrode for comparison.

[0082] In any of the following experiments, a two - electrode system was used to test the stability of oxygen evolution in the water electrolysis of the acid - insoluble metal oxide - doped ruthenium oxide nanomaterial of the present invention and obtain a stability curve. In the two - electrode system, a platinum sheet electrode was used as the cathode, and the acid - insoluble metal oxide - doped ruthenium oxide nanomaterial obtained in the example was used as the anode. When it is necessary to make a comparison, the following specific other materials are used as the working electrode for comparison. Example 1 - Sol - gel method

[0083] The method for manufacturing the niobium - doped ruthenium oxide nanomaterial includes the following steps. (1) An ethanol solution of ruthenium chloride and an ethanol solution of niobium chloride were put into a glass reactor, and the concentration of ruthenium chloride in the glass reactor was controlled to be 0.1 mol / L, and the concentration of niobium chloride was controlled to be 0.025 mol / L. The glass reactor was capped and sealed to prevent the hydrolysis of the precursor. The sealed glass reactor was dispersed for 3 h under ultrasonic treatment conditions to obtain a metal ethanol solution of uniform color. Next, polyvinylpyrrolidone powder (the concentration of polyvinylpyrrolidone as the ligand was controlled to be 40 g / L) was added to the solution, and ultrasonic treatment was carried out for 1 h while sealed to obtain a mixed solution of uniform color. Then, the glass reactor was placed in a constant - temperature oil - bath pan and kept warm at 70 °C for 12 h. Next, the cap was removed and the solvent was evaporated to obtain a metal powder precursor of uniform color. (2) After putting the metal powder precursor obtained in step (1) into a boat, the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set at 10 °C / min, heated to 400 °C, held for 5 h, then naturally cooled to obtain a black powder sample, which was washed multiple times with deionized water and ethanol and dried to obtain the niobium-doped ruthenium oxide nanomaterial with a niobium doping amount of 20%. The calculation formula for the niobium doping amount is N niobium / (N niobium + N ruthenium) = 1 / 5 = 20%. Characterization of Niobium-Doped Ruthenium Oxide Nanomaterials As shown in Fig. 1 for the scanning electron microscope image of the obtained niobium-doped ruthenium oxide nanomaterial, its XRD spectrum is shown in Fig. 2. From Fig. 1, it was found that the niobium-doped ruthenium oxide nanomaterial has a very small particle size of 50 - 200 nm, is very uniform, and has a rough and porous surface. The XRD spectrum of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Fig. 2. From Fig. 2, it was found that the niobium-doped ruthenium oxide nanomaterial shows characteristic peaks of rutile-phase ruthenium oxide. Compared with the standard card of rutile-phase ruthenium oxide, the diffraction peaks of niobium-doped ruthenium oxide shift in the direction of a smaller angle, and no diffraction peak of niobium oxide is found. From this, it is clear that the niobium element is successfully doped into the lattice of ruthenium oxide without phase separation. That is, in the niobium-doped ruthenium oxide nanomaterial, niobium is doped into the interior of the ruthenium oxide crystal and replaces a part of the positions of ruthenium in the lattice. Therefore, from Fig. 2, the molecular formula of the material is Nb x Ru 1-x O 2 was confirmed. The elemental distribution diagram of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 3. From Figure 3, it was found that the elements of the niobium-doped ruthenium oxide nanomaterial are uniformly distributed, and in particular, the distributions of niobium and ruthenium are consistent throughout the particles. From this, it became clear that niobium is uniformly dispersed within the ruthenium oxide crystal. Therefore, in the said niobium-doped ruthenium oxide nanomaterial, both niobium and ruthenium are uniformly dispersed. Example 2 - Sol-gel method

[0084] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to an ethyl niobate aqueous solution, and polyvinylpyrrolidone was changed to polyvinyl alcohol. By changing the usage amounts of ruthenium chloride and ethyl niobate, in a glass reactor, the concentration of the ruthenium chloride ethanol solution was controlled to 1 mol / L, and the solubility of the ethyl niobate aqueous solution was controlled to 0.01 mol / L. As the roasting conditions of the said muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 5 hours. The doping amount of niobium in the niobium-doped ruthenium oxide nanomaterial is 1%. The calculation formula for the doping amount of niobium is N niobium / (N niobium + N ruthenium) = 0.001 / 0.1 = 1%. The scanning electron microscope image of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 4. Example 3 - Sol-gel method

[0085] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to an ethyl niobate aqueous solution, and polyvinylpyrrolidone was changed to polyethylene glycol. By changing the usage amounts of ruthenium chloride and ethyl niobate, in a glass reactor, the concentration of the ruthenium chloride ethanol solution was controlled to 1 mol / L, and the solubility of the ethyl niobate aqueous solution was controlled to 1 mol / L. The doping amount of niobium in the niobium-doped ruthenium oxide nanomaterial is 50%. As the roasting conditions of the said muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 5 hours. The doping amount of niobium in the niobium-doped ruthenium oxide nanomaterial is 50%. The calculation formula for the doping amount of niobium is N niobium / (N niobium + N ruthenium) = 25 / 50 = 50%. A high-resolution electron microscope image 5 of the niobium-doped ruthenium oxide nanomaterial is obtained. In the figure, 0.317 nm corresponds to the 110 crystal plane of ruthenium oxide. Example 4 - Sol-gel method

[0086] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to an aqueous solution of ethyl niobate, and polyvinylpyrrolidone was changed to polyethylene diamine. By changing the usage amounts of ruthenium chloride and ethyl niobate, the concentration of the ruthenium chloride ethanol solution in a glass reactor was controlled to 0.8 mol / L, and the solubility of the aqueous solution of ethyl niobate was controlled to 0.2 mol / L. As the baking conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 5 hours. The doping amount of niobium in the niobium-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of niobium is N niobium / (N niobium + N ruthenium) = 2 / 10 = 20%. The high-resolution electron microscope image of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 6. In the figure, 0.256 and 0.316 nm correspond to the 101 and 110 crystal planes of ruthenium oxide, and it was found that the doping amount of niobium decreased. Compared with Example 3, in Example 4, the lattice spacing decreased. Example 5 - Sol-gel method

[0087] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to an aqueous solution of niobium carbonyl, and polyvinylpyrrolidone was changed to polylactic acid. By changing the usage amounts of ruthenium chloride and niobium carbonyl, the concentration of the ruthenium chloride ethanol solution in a glass reactor was controlled to 0.8 mol / L, and the solubility of the aqueous solution of niobium carbonyl was controlled to 0.2 mol / L. As the baking conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 5 hours. The doping amount of niobium in the niobium-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of niobium is Nniobium / (Nniobium + Nruthenium) = 2 / 10 = 20%. The scanning electron microscope image of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 7. Example 6 - Sol-gel method

[0088] Referring to the method of Example 1, polyvinylpyrrolidone was changed to polypyridine, niobium chloride ethanol solution was changed to ammonium niobium oxalate aqueous solution, and ruthenium chloride was changed to acetylacetonato ruthenium. The usage amount of ethylenediaminetetraacetic acid was changed to 60 mg, that is, the concentration of the ligand was controlled to 1 g / L. As the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the heat preservation temperature was 500 °C, and the heat preservation time was 6 hours. The doping amount of niobium in the niobium-doped ruthenium oxide nanomaterial is 20%. The scanning electron microscope image of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 8. From Figure 8, it was found that the niobium-doped ruthenium oxide nanomaterial has a small particle size of 50 - 200 nm, is very uniform, and has a rough and porous surface. Example 7 - Sol-gel method

[0089] Referring to the method of Example 1, niobium chloride ethanol solution was changed to niobium oxalate aqueous solution, and polyvinylpyrrolidone was changed to polyamide. Ruthenium chloride was replaced with ruthenium(III) nitrosyl nitrate. The doping amount of niobium in the niobium-doped ruthenium oxide nanomaterial is 20%. The scanning electron microscope of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 9. From Figure 9, it was found that the niobium-doped ruthenium oxide nanomaterial has a small particle size of 50 - 200 nm, is very uniform, and has a rough and porous surface. Example 8 - Solvothermal method

[0090] (1) An aqueous solution of ruthenium chloride and niobium oxalate was placed in a 40 ml hydrothermal treatment kettle, and ultrasonic treatment was carried out for 15 minutes in a glass reactor until all the precursors were dissolved, with the concentration of ruthenium chloride being 0.1 mol / L and the concentration of niobium oxalate being 0.001 mol / L. 4 mol / L of urea was added, the hydrothermal treatment kettle was placed in a constant temperature air circulation oven at 100 °C, kept warm for 8 hours, the hydrothermal treatment kettle was taken out, and after natural cooling to room temperature, the precipitate formed by the reaction was taken out, centrifuged with deionized water and washed several times, and then placed in an oven at 80 °C and baked. (2) The above baked powder sample was placed in a boat, the boat was placed in a muffle furnace, the heating rate was set at 5 °C / min, heated to 400 °C, kept warm for 2 h, then naturally cooled, and the niobium-doped ruthenium oxide nanomaterial with a niobium doping amount of 1% was obtained as a black powder sample. The calculation formula for the niobium doping amount is N niobium / (N niobium + N ruthenium) = 1 / 101 = 1%. The XRD pattern of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 10. From Figure 10, it was found that the niobium element was successfully doped into the lattice such as ruthenium oxide. That is, the niobium in the niobium-doped ruthenium oxide nanomaterial is doped into the inside of the ruthenium oxide lattice and replaces a part of the position of ruthenium in the lattice. Therefore, from Figure 10, the molecular formula of the material is Nb x Ru 1-x O 2 was confirmed. Example 9 - Solvothermal Method

[0091] (1) An aqueous solution of ruthenium chloride and niobium oxalate was placed in a 40 ml hydrothermal treatment kettle, and ultrasonic treatment was carried out for 15 minutes in a glass reactor until all the precursors were dissolved, with the concentration of ruthenium chloride being 1 mol / L and the concentration of niobium oxalate being 1 mol / L. 0.1 mol / L of ammonia water was added, the hydrothermal treatment kettle was placed in a constant temperature air circulation oven at 200 °C, kept warm for 16 hours, the hydrothermal treatment kettle was taken out, and after natural cooling to room temperature, the precipitate formed by the reaction was taken out, centrifuged with deionized water and washed several times, and then placed in an oven at 80 °C and baked. (2) Put the above-baked powder sample into a boat, place the boat in a muffle furnace, set the heating rate to 10 °C / min, heat it up to 600 °C, keep it warm for 8 h, then let it cool naturally, and obtain the niobium-doped ruthenium oxide nanomaterial with a niobium doping amount of 50% as a black powder sample. The calculation formula for the niobium doping amount is N niobium / (N niobium + N ruthenium) = 1 / 2 = 50%. The XRD pattern of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 11. From Figure 11, it was found that the niobium element was successfully doped into the lattice of ruthenium oxide, for example. That is, the niobium in the niobium-doped ruthenium oxide nanomaterial is doped into the interior of the ruthenium oxide lattice, replacing a part of the position of ruthenium in the lattice. Therefore, from Figure 11, the molecular formula of the material is Nb x Ru 1-x O 2 It was confirmed that it is. Example 10 - Ball milling method

[0092] Put 9 mol of ruthenium oxide and 9 mol of niobium pentoxide into a 40 ml ball milling tank and mix them uniformly. Perform ball milling twice for 6 hours each. Put the above uniformly ball-milled precursor powder sample into a boat, place the boat in a muffle furnace, set the heating rate to 5 - 10 °C / min, heat it up to 800 °C, keep it warm for 6 h, then let it cool naturally, and obtain the niobium-doped ruthenium oxide nanomaterial with a niobium doping amount of 50% as a black powder sample. The calculation formula for the niobium doping amount is N niobium / (N niobium + N ruthenium) = 9 / 18 = 50%. The XRD of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 12. From Figure 12, it was found that the crystal structure of ruthenium oxide was maintained as its crystal structure. Nb x Ru 1-x O 2 It is represented as. Example 11 - Ball milling method

[0093] 9.9 mol of ruthenium oxide and 0.1 mol of niobium pentoxide were placed in a 40 ml ball milling tank, and ball milling was carried out three times for 3 hours each to uniformly mix the precursors. The powder sample of the uniformly ball-milled precursor was put into a boat, the boat was put into a muffle furnace, the heating rate was set at 5 - 10 °C / min, heated to 400 °C, kept warm for 12 h, then naturally cooled to obtain the niobium-doped ruthenium oxide nanomaterial with a niobium doping amount of 10% as a black powder sample. The calculation formula for the niobium doping amount is N niobium / (N niobium + N ruthenium) = 0.1 / 10 = 1%. The scanning electron microscope image of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Figure 13. From Figure 13, it was found that it is porous and remains in the size range of 50 - 200 nm. Example 12 - Titanium-doped ruthenium oxide

[0094] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to a titanium chloride ethanol solution. In a glass reactor, the concentration of the ruthenium chloride ethanol solution was controlled at 1 mol / L, and the solubility of the titanium chloride solution was controlled at 0.25 mol / L. As the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 5 hours. The doping amount of titanium in the titanium-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the titanium doping amount is N titanium / (N titanium + N ruthenium) = 0.25 / 1.25 = 20%. The XRD pattern of the titanium-doped ruthenium oxide nanomaterial obtained in Example 12 is shown in Figure 14. From Figure 14, it was found that the titanium element was successfully doped into the lattice of ruthenium oxide, for example. That is, the titanium was doped into the interior of the lattice in the ruthenium oxide nanomaterial and replaced a part of the position of ruthenium in the lattice. Therefore, from Figure 14, the molecular formula of the material is Ti x Ru 1-x O 2 was confirmed. Example 13 - Zirconium-doped ruthenium oxide

[0095] (1) Put an aqueous solution of ruthenium chloride and zirconium chloride into a 40 ml hydrothermal reactor, and perform ultrasonic treatment in a glass reactor for more than 15 minutes until all the precursors are dissolved. Set the concentration of ruthenium chloride to 1 mol / L and the concentration of zirconium chloride to 0.25 mol / L. Add 0.2 g of aqueous ammonia, put the hydrothermal reactor into a constant temperature air oven at 200 °C, keep it warm for 16 hours, take out the hydrothermal reactor, let it cool naturally to room temperature, then take out the precipitate generated by the reaction, centrifuge it with deionized water and wash it several times, and then put it into an oven at 80 °C and bake it. (2) Put the above baked powder sample into a boat, put the boat into a muffle furnace, set the heating rate to 10 °C / min, heat it up to 600 °C, keep it warm for 8 h, then cool it naturally, and obtain the zirconium-doped ruthenium oxide nanomaterial with a zirconium doping amount of 20% as a black powder sample. The calculation formula for the zirconium doping amount is Nzirconium / (Nzirconium + Nruthenium) = 0.25 / 1.25 = 20%. The XRD pattern of the obtained zirconium-doped ruthenium oxide nanomaterial is shown in Figure 15. From Figure 15, it was found that the zirconium element is doped, for example, into the lattice of ruthenium oxide. That is, the zirconium in the zirconium-doped ruthenium oxide nanomaterial is doped into the interior of the ruthenium oxide lattice and replaces part of the position of ruthenium in the lattice. Therefore, from Figure 15, the molecular formula of the material is Zr x Ru 1-x O 2 It was confirmed that it is. Example 14 - Hafnium-doped ruthenium oxide

[0096] 8 mol of ruthenium oxide and 2 mol of hafnium oxide were placed in a 40 ml ball milling tank and mixed uniformly. Ball milling was carried out twice for 6 hours each. The uniformly ball-milled precursor powder sample was placed in a boat, and the boat was placed in a muffle furnace. The heating rate was set at 5 - 10 °C / min, and the temperature was raised to 800 °C, held for 6 h, then naturally cooled to obtain the hafnium-doped ruthenium oxide nanomaterial with a hafnium doping amount of 20% as a black powder sample. The calculation formula for the hafnium doping amount is N hafnium / (N hafnium + N ruthenium) = 2 / 10 = 20%. The XRD of the obtained hafnium-doped ruthenium oxide nanomaterial is shown in Fig. 16. It can be seen from Fig. 16 that the crystal structure of ruthenium oxide was maintained as its crystal structure. Hf x Ru 1-x O 2 is represented as. Example 15 - Tungsten-doped ruthenium oxide

[0097] 8 mol of ruthenium oxide and 2 mol of tungsten oxide were placed in a 40 ml ball milling tank and mixed uniformly. Ball milling was carried out twice for 6 hours each. The uniformly ball-milled precursor powder sample was placed in a boat, and the boat was placed in a muffle furnace. The heating rate was set at 5 - 10 °C / min, and the temperature was raised to 800 °C, held for 6 h, then naturally cooled to obtain the tungsten-doped ruthenium oxide nanomaterial with a tungsten doping amount of 20% as a black powder sample. The calculation formula for the tungsten doping amount is N tungsten / (N tungsten + N ruthenium) = 2 / 10 = 20%. The XRD of the obtained tungsten-doped ruthenium oxide nanomaterial is shown in Fig. 17. It can be seen from Fig. 17 that the crystal structure of ruthenium oxide was maintained as its crystal structure. W x Ru 1-x O 2 is represented as. Example 16 - Molybdenum-doped ruthenium oxide

[0098] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to a molybdenum chloride ethanol solution. In a glass reactor, the concentration of the ruthenium chloride ethanol solution was controlled at 1 mol / L, and the solubility of the molybdenum chloride solution was controlled at 0.25 mol / L. As for the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 5 hours. The doping amount of molybdenum in the molybdenum-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of molybdenum is Nmolybdenum / (Nmolybdenum + Nruthenium) = 0.25 / 1.25 = 20%. The XRD pattern of the obtained molybdenum-doped ruthenium oxide nanomaterial is shown in FIG. 18. From FIG. 18, it was found that the molybdenum element was successfully doped into the lattice of ruthenium oxide, for example. That is, the molybdenum in the molybdenum-doped ruthenium oxide nanomaterial is doped into the interior of the ruthenium oxide lattice and replaces part of the position of ruthenium in the lattice. Therefore, from FIG. 18, the molecular formula of the material is Mo x R u1-x O 2 It was confirmed that it is. Example 17 - Tantalum-doped ruthenium oxide

[0099] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to a tantalum chloride ethanol solution. In a glass reactor, the concentration of the ruthenium chloride ethanol solution was controlled at 1 mol / L, and the solubility of the tantalum chloride solution was controlled at 0.25 mol / L. As for the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 5 hours. The doping amount of tantalum in the tantalum-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of tantalum is Ntantalum / (Ntantalum + Nruthenium) = 0.25 / 1.25 = 20%. The XRD pattern of the obtained tantalum-doped ruthenium oxide nanomaterial is shown in FIG. 19. From FIG. 19, it was found that the tantalum element is doped, for example, into the lattice of ruthenium oxide. That is, tantalum in the tantalum-doped ruthenium oxide nanomaterial is doped inside the ruthenium oxide lattice and replaces part of the position of ruthenium in the lattice. Therefore, from FIG. 19, the molecular formula of the material was found to be Ta x Ru 1-x O 2 It was confirmed that it is. Application Example 1

[0100] Using a silver / silver chloride electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the niobium-doped ruthenium oxide nanomaterial obtained in Examples 1 to 3 or commercially available ruthenium dioxide as the working electrode, in a 0.5 mol / L sulfuric acid solution, the oxygen evolution characteristics of the niobium-doped ruthenium oxide nanomaterial of the present invention in water electrolysis were tested, and the obtained polarization curve is shown in FIG. 20. From FIG. 20, the niobium-doped ruthenium oxide nanomaterials obtained in Examples 1 to 3 are excellent in oxygen evolution characteristics (curves A-C in FIG. 20) in water electrolysis, and are clearly superior to the commercially available ruthenium dioxide material (curve D in FIG. 20). At a current density of 10 mA / cm 2 The overpotentials were 196 mV, 219, and 240 mV in order, which was found to be lower than the overpotential of 320 mV of commercially available ruthenium dioxide. Application Example 2

[0101] FIG. 21 is a stability curve in a 0.5 mol / L H 2 SO 4 solution when used as an oxygen evolution anode material of the niobium-doped ruthenium oxide material obtained in Example 1 and Example 2 of the present invention. Here, curve A is the stability curve at a current density of 100 mA / cm 2 of the niobium-doped ruthenium oxide material obtained in Example 1, and curve B is the stability curve at a current density of 100 mA / cm 2Stability curves at current density. The C curve is the stability curve of the niobium-doped ruthenium oxide material obtained in Example 1 at 200 mA / cm 2 Stability curves at current density. The D curve is the stability curve of the niobium-doped ruthenium oxide material obtained in Example 2 at 200 mA / cm 2 Stability curves at current density. From Figure 21, when held for 360 hours at current densities of 100 and 200 mA / cm 2 it was found that the current in the niobium-doped ruthenium oxide nanomaterials obtained in Example 1 and Example 2 had hardly decayed. From this, it became clear that the niobium-doped ruthenium oxide nanomaterial has extremely high stability at high current densities when used as an oxygen evolution reaction anode material. Application Example 3

[0102] Using a silver / silver chloride electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the niobium-doped ruthenium oxide nanomaterial obtained in Example 5 or commercially available ruthenium dioxide as the working electrode, the oxygen evolution characteristics in the water electrolysis of the niobium-doped ruthenium oxide nanomaterial of the present invention were tested in a 0.5 mol / L sulfuric acid solution, and the obtained polarization curve is shown in Figure 22. From Figure 22, it was found that the overvoltage of the niobium-doped ruthenium oxide nanomaterial produced in Example 5 at 10 mA / cm 2 for the oxygen evolution reaction is 200 mV (curve A in Figure 22), which is much lower than 320 mV (curve B in Figure 22) of commercially available ruthenium dioxide. From this, it was confirmed that the niobium-doped ruthenium oxide obtained in Example 5 is superior in oxygen evolution reaction activity to commercially available ruthenium dioxide. Application Example 4

[0103] Using a silver / silver chloride electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the acid-insoluble metal oxide-doped ruthenium oxide nanomaterials obtained in Examples 6, 7, 8, 10, and 12 to 17 or commercially available ruthenium dioxide as the working electrode, the oxygen evolution reaction activity in the water electrolysis of the niobium-doped ruthenium oxide nanomaterial of the present invention was tested. Using the acid-insoluble metal oxide-doped ruthenium oxide nanomaterials obtained in Examples 6, 7, 8, 10, and 12 to 17 as anodes or commercially available ruthenium dioxide, and a platinum sheet electrode as a cathode, the stability of the oxygen evolution reaction in the water electrolysis of the acid-insoluble metal oxide-doped ruthenium oxide nanomaterials of the present invention was tested by a two-electrode system.

[0104] Figure 23 is a polarization curve obtained by testing the niobium-doped ruthenium oxide nanomaterial obtained in Example 6 and commercially available ruthenium dioxide in a 0.5 mol / L sulfuric acid solution. From Figure 23, it was found that the niobium-doped ruthenium oxide nanomaterial produced in Example 6 had an overvoltage of 226 mV at 10 mA / cm 2 in the oxygen evolution reaction (curve A in Figure 23), which was lower than the overvoltage of 320 mV of commercially available ruthenium dioxide (curve B in Figure 23). From this, it was confirmed that the niobium-doped ruthenium oxide produced in Example 6 had more excellent oxygen evolution reaction activity.

[0105] Figure 24 is a polarization curve obtained by testing the niobium-doped ruthenium oxide material obtained in Example 7 and commercially available ruthenium dioxide in a 0.5 mol / L sulfuric acid solution. From Figure 24, it was found that the niobium-doped ruthenium oxide nanomaterial produced in Example 7 had an overvoltage of 210 mV at 10 mA / cm 2 in the oxygen evolution reaction (curve A in Figure 24), which was lower than the overvoltage of 320 mV of commercially available ruthenium dioxide (curve B in Figure 24). From this, it was confirmed that the niobium-doped ruthenium oxide produced in Example 7 had more excellent oxygen evolution reaction activity.

[0106] Figure 25 is a polarization curve obtained by testing the niobium-doped ruthenium oxide material obtained in Example 8 and commercially available ruthenium dioxide in a 0.5 mol / L sulfuric acid solution. From Figure 25, it was found that the niobium-doped ruthenium oxide nanomaterial produced in Example 8 had an overvoltage of 10 mA / cm 2The overvoltage at [the specified condition] was 170 mV (curve A in Fig. 25), which was lower than the overvoltage of 320 mV of commercially available ruthenium dioxide (curve B in Fig. 25). From this, it was confirmed that the niobium-doped ruthenium oxide produced in Example 8 has more excellent oxygen evolution reaction activity.

[0107] Fig. 26 is a polarization curve obtained by testing the niobium-doped ruthenium oxide material obtained in Example 10 and commercially available ruthenium dioxide in a 0.5 mol / L sulfuric acid solution. From Fig. 26, for the niobium-doped ruthenium oxide nano-material produced in Example 10, the overvoltage at 10 mA / cm 2 was 240 mV (curve A in Fig. 26), which was lower than the overvoltage of 320 mV of commercially available ruthenium dioxide (curve B in Fig. 26). From this, it was confirmed that the niobium-doped ruthenium oxide produced in Example 10 has more excellent oxygen evolution reaction activity.

[0108] Fig. 27 is a stability curve of the niobium-doped ruthenium oxide material obtained in Example 5 at a current density of 100 mA / cm 2 . From Fig. 27, it was found that when maintained at a current density of 100 mA / cm 2 for 100 hours, the current of the niobium-doped ruthenium oxide nano-material obtained in Example 5 hardly decayed. From this, it became clear that when the niobium-doped ruthenium oxide nano-material is used as an oxygen evolution reaction anode material, it has very high stability at high current densities.

[0109] Fig. 28 is a stability curve of the niobium-doped ruthenium oxide material obtained in Example 7 at a current density of 100 mA / cm 2 . From Fig. 28, it was found that when maintained at a current density of 100 mA / cm 2 for 25 hours, the current of the niobium-doped ruthenium oxide nano-material obtained in Example 7 hardly decayed. From this, it became clear that when the niobium-doped ruthenium oxide nano-material is used as an oxygen evolution reaction anode material, it has very high stability at high current densities.

[0110] Figure 29 shows the stability curve of the niobium-doped ruthenium oxide material obtained in Example 8 at a current density of 100 mA / cm 2 From Figure 29, it was found that when maintained at a current density of 100 mA / cm 2 for 45 hours, the current of the niobium-doped ruthenium oxide nanomaterial obtained in Example 8 hardly decayed. From this, it was revealed that the niobium-doped ruthenium oxide nanomaterial has very high stability at high current densities when used as an oxygen evolution reaction anode material.

[0111] Figure 30 shows the stability curve of the niobium-doped ruthenium oxide material obtained in Example 10 at a current density of 100 mA / cm 2 From Figure 30, it was found that when maintained at a current density of 100 mA / cm 2 for 80 hours, the current of the niobium-doped ruthenium oxide nanomaterial obtained in Example 10 hardly decayed. From this, it was revealed that the niobium-doped ruthenium oxide nanomaterial has very high stability at high current densities when used as an oxygen evolution reaction anode material.

[0112] Figure 31 shows the polarization curves obtained by testing the metal-doped ruthenium oxide materials obtained in Examples 12 to 17 in a 0.5 mol / L sulfuric acid solution. From Figure 31, the titanium-doped ruthenium oxide nanomaterial produced in Example 12 has an overpotential of 194 mV at 10 mA / cm 2 in the oxygen evolution reaction (curve B in Figure 31), and the zirconium-doped ruthenium oxide nanomaterial produced in Example 13 has an overpotential of 200 mV at 10 mA / cm 2 in the oxygen evolution reaction (curve F in Figure 31), and the hafnium-doped ruthenium oxide nanomaterial produced in Example 14 has an overpotential of 210 mV at 10 mA / cm 2 in the oxygen evolution reaction (curve C in Figure 31), and the tungsten-doped ruthenium oxide nanomaterial produced in Example 15 has an overpotential of 10 mA / cm 2The overvoltage at [specific condition] is 214 mV (curve D in Fig. 31). The molybdenum-doped ruthenium oxide nanomaterial produced in Example 16 has an overvoltage of 10 mA / cm 2 The overvoltage at [specific condition] is 194 mV (curve A in Fig. 31). The tantalum-doped ruthenium oxide nanomaterial produced in Example 17 has an overvoltage of 10 mA / cm 2 The overvoltage at [specific condition] is 209 mV (curve E in Fig. 31). It was found that all of these are lower than the overvoltage of 320 mV of commercially available ruthenium dioxide (curve B in Fig. 26). From this, it was confirmed that the metal-doped ruthenium oxides produced in Examples 12 to 17 have more excellent oxygen evolution reaction activity.

[0113] Fig. 32 is the stability curve at a current density of 100 mA / cm of the metal-doped ruthenium oxide materials obtained in Examples 12 to 17. 2 A is the stability curve of titanium-doped ruthenium oxide produced in Example 12, D is the stability curve of zirconium-doped ruthenium oxide produced in Example 13, C is the stability curve of hafnium-doped ruthenium oxide produced in Example 14, F is the stability curve of tungsten-doped ruthenium oxide produced in Example 15, B is the stability curve of molybdenum-doped ruthenium oxide produced in Example 16, and E is the stability curve of tantalum-doped ruthenium oxide produced in Example 17. From Fig. 32, it was found that when maintained at a current density of 100 mA / cm 2 for 60 hours, the current of the metal-doped ruthenium oxide nanomaterials obtained in Examples 12 to 17 hardly decays. From this, it became clear that the above metal-doped ruthenium oxide nanomaterials have very high stability at high current densities when used as oxygen evolution reaction anode materials.

[0114] Fig. 33 is the constant current test curve at a current density of 100 mA / cm of commercially available ruthenium dioxide, and it decayed by more than 500 mV after a 1-hour test. 2

[0115] From FIGS. 19 to 34, it was shown that the niobium-doped ruthenium oxide nanomaterial of the present invention has excellent activity and stability in oxygen evolution in water electrolysis, and is superior to commercially available ruthenium dioxide materials in all cases.

[0116] From the above, it was fully confirmed that niobium can be doped into the ruthenium oxide lattice by a simple method to obtain a niobium-doped ruthenium oxide nanomaterial. The niobium-doped ruthenium oxide nanomaterial has a rough nanostructure on the surface and excellent electrochemically oxygen evolution reaction characteristics. Comparative Example 1

[0117] In order to improve the stability of the acid-insoluble metal-doped catalyst, referring to the production method of Example 1, niobium chloride was changed to iron chloride to produce an iron-doped ruthenium oxide nanomaterial. The iron-doped ruthenium oxide nanomaterial was tested as an oxygen evolution reaction anode material, and the polarization curve and stability curve obtained by the test are shown in FIGS. 34 and 35. As shown in FIG. 34, curve A is the polarization curve of the oxygen evolution reaction of the iron-doped ruthenium oxide nanomaterial obtained in Comparative Example 1, and curve B is the polarization curve of the oxygen evolution reaction of the niobium-doped ruthenium oxide nanomaterial obtained in Example 1. From FIG. 34, at 10 mA / cm 2 it was found that the overpotential of niobium-doped ruthenium oxide is 196 mV, while that of iron-doped ruthenium oxide is 320 mV. Therefore, niobium-doped ruthenium oxide had higher oxygen evolution reaction activity. FIG. 35 is the stability curve of iron-doped ruthenium oxide obtained in Comparative Example 1 at a current density of 100 mA / cm 2 From FIG. 35, after 1 hour, the stability curve showed a decay of more than 300 mV, indicating that the stability of the iron-doped ruthenium oxide nanomaterial is poor. Therefore, the iron-doped ruthenium oxide nanomaterial of Comparative Example 1 has a large difference in stability compared with the niobium-doped ruthenium oxide obtained in Example 1, and the excellent stability of the niobium-doped ruthenium oxide oxygen evolution reaction was further confirmed. Example 18-3 Metal-Doped Ruthenium Oxide

[0118] Referring to the method of Example 1, the niobium chloride ethanol solution was changed to an ethanol solution of molybdenum chloride, titanium chloride, and niobium chloride. In a glass reactor, the concentration of ruthenium chloride ethanol solution was 1 mol / L, and the total solubility of molybdenum chloride, titanium chloride, and niobium chloride solutions was controlled to 0.25 mol / L (specifically, molybdenum chloride, titanium chloride, and niobium chloride were all 0.083 mol). As the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the heat preservation temperature was 400 °C, and the heat preservation time was 5 hours. The doping amount of molybdenum in the molybdenum-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of molybdenum is (N_molybdenum + N_titanium + N_niobium) / (N_molybdenum + N_titanium + N_niobium + N_ruthenium)=0.25 / 1.25 = 20%. The XRD pattern of the obtained three-metal-doped ruthenium oxide nanomaterial is shown in Figure 36. From Figure 36, it was found that three elements of molybdenum, titanium, and niobium were successfully doped into the lattice of ruthenium oxide, for example. That is, molybdenum, titanium, and niobium in the molybdenum-doped ruthenium oxide nanomaterial are doped into the interior of the ruthenium oxide lattice, replacing a part of the position of ruthenium in the lattice. Therefore, from Figure 36, the molecular formula of the material is (TiNbMo) x Ru 1-x O 2 It was confirmed that it is. Example 19 - Five-metal-doped ruthenium oxide

[0119] (1) An aqueous solution of ruthenium chloride, zirconium chloride, niobium chloride, titanium chloride, molybdenum chloride, and tungsten chloride was placed in a 40 ml hydrothermal treatment kettle, and ultrasonic treatment was performed for more than 15 minutes in a glass reactor until all the precursors were dissolved. The concentration of ruthenium chloride was 1 mol / L, and the total concentration of zirconium chloride, niobium chloride, titanium chloride, molybdenum chloride, and tungsten chloride was 0.25 mol / L (specifically, 0.05 mol of each of zirconium chloride, niobium chloride, titanium chloride, molybdenum chloride, and tungsten chloride). 0.2 g of aqueous ammonia was added, the hydrothermal treatment kettle was placed in a constant temperature air blast oven at 200 °C, kept warm for 16 hours, the hydrothermal treatment kettle was taken out, and after natural cooling to room temperature, the precipitate formed by the reaction was taken out, centrifuged with deionized water and washed several times, and then placed in an oven at 80 °C and baked. (2) The above baked powder sample was placed in a boat, the boat was placed in a muffle furnace, the heating rate was set at 10 °C / min, heated to 600 °C, kept warm for 8 h, then naturally cooled, and the zirconium-doped ruthenium oxide nanomaterial with a metal doping amount of 20% was obtained as a black powder sample. The calculation formula for the zirconium doping amount is (Nzirconium + Nniobium + Ntitanium + Nmolybdenum + Ntungsten) / (Nzirconium + Nniobium + Ntitanium + Nmolybdenum + Ntungsten + Nruthenium)=0.25 / 1.25 = 20%. The XRD pattern of the obtained five-metal-doped ruthenium oxide nanomaterial is shown in Fig. 37. From Fig. 37, it was found that the five elements were successfully doped into the lattice of ruthenium oxide, for example. That is, the five metals in the five-metal-doped ruthenium oxide nanomaterial are doped into the interior of the ruthenium oxide lattice, replacing a part of the position of ruthenium in the lattice. Therefore, from Fig. 37, it was confirmed that the molecular formula of the material is (NbZrTiMoW) x Ru 1-x O 2 It was confirmed that it is. Example 20 - Seven-metal-doped ruthenium oxide

[0120] Ruthenium oxide, titanium oxide, niobium oxide, tantalum oxide, zirconium oxide, hafnium oxide, molybdenum oxide, and tungsten oxide were placed in a 40 ml ball milling tank and uniformly mixed. The ruthenium oxide was 8 mol, and the total of titanium oxide, niobium oxide, tantalum oxide, zirconium oxide, hafnium oxide, molybdenum oxide, and tungsten oxide was 2 mol (specifically, each of titanium oxide, niobium oxide, tantalum oxide, zirconium oxide, hafnium oxide, molybdenum oxide, and tungsten oxide was 0.0355 mol). Ball milling was performed twice for 6 hours each. The uniformly ball-milled precursor powder sample was placed in a boat, and the boat was placed in a muffle furnace. The heating rate was set at 5 - 10 °C / min, heated to 800 °C, held for 6 h, and then naturally cooled to obtain the tungsten-doped ruthenium oxide nanomaterial with a tungsten doping amount of 20% as a black powder sample. The calculation formula for the tungsten doping amount is (N zirconium + N niobium + N titanium + N molybdenum + N tungsten + N hafnium + N tantalum) / (N zirconium + N niobium + N titanium + N molybdenum + N tungsten + N hafnium + N tantalum + N ruthenium) = 2 / 10 = 20%. The XRD of the obtained 7-metal-doped ruthenium oxide nanomaterial is shown in Fig. 38. From Fig. 38, it was found that the crystal structure of ruthenium oxide was maintained as its crystal structure. (TiHfZrNbTaWMo) x Ru 1-x O 2 is represented as. For the production of other ruthenium oxide nanomaterials doped with 2, 4, or 6 kinds of metals, Examples 18, 19, or 20 can be referred to. Application Example 5

[0121] Fig. 39 is a polarization curve obtained by testing the metal-doped ruthenium oxide materials obtained in Examples 18 - 20 in a 0.5 mol / L sulfuric acid solution. From Fig. 39, the 3-metal-doped ruthenium oxide nanomaterial produced in Example 18 has a current density of 10 mA / cm 2The overvoltage at [value] is 242 mV (curve A in Fig. 39). The zirconium-doped ruthenium oxide nanomaterial produced in Example 19 has an overvoltage of 231 mV (curve B in Fig. 39) at 10 mA / cm 2 in the oxygen evolution reaction. The hafnium-doped ruthenium oxide nanomaterial produced in Example 20 has an overvoltage of 235 mV (curve C in Fig. 39) at 10 mA / cm 2 in the oxygen evolution reaction. It was found that all of these are lower than the overvoltage of 320 mV (curve D in Fig. 39) of commercially available ruthenium dioxide. From this, it was confirmed that the metal-doped ruthenium oxides produced in Examples 18 to 20 have more excellent oxygen evolution reaction activity. Application Example 6

[0122] Fig. 40 is the stability curve at a current density of 100 mA / cm for the metal-doped ruthenium oxide materials obtained in Examples 18 to 20. A is the stability curve of molybdenum-titanium-niobium-doped ruthenium oxide produced in Example 18, B is the stability curve of zirconium-tungsten-molybdenum-titanium-niobium-doped ruthenium oxide produced in Example 19, and C is the stability curve of molybdenum-titanium-niobium-zirconium-hafnium-tantalum-tungsten-doped ruthenium oxide produced in Example 20. From Fig. 40, it was found that when held at a current density of 100 mA / cm 2 for 50 hours, the current of the metal-doped ruthenium oxide nanomaterials obtained in Examples 18 to 20 hardly decays. From this, it became clear that the above metal-doped ruthenium oxide nanomaterials have very high stability at high current densities when used as oxygen evolution reaction anode materials. 2 Comparative Example 2

[0123] In order to improve the action of the polymer multidentate ligand in the synthesis of the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, a niobium-doped ruthenium oxide nanomaterial was produced in the same manner as the production method of Example 1 except that vinylpyrrolidone was changed to citric acid. The XRD pattern of the obtained niobium-doped ruthenium oxide nanomaterial is shown in Fig. 41. From FIG. 41, it was found that niobium was successfully doped into the lattice of ruthenium oxide, for example. That is, niobium in the molybdenum-doped ruthenium oxide nanomaterial is doped inside the ruthenium oxide lattice, replacing a part of the position of ruthenium in the lattice. Therefore, from FIG. 41, the molecular formula of the material is (TiNbMo) x Ru 1-x O 2 was confirmed to be the case. Using the niobium-doped ruthenium oxide nanomaterial produced in Comparative Example 2 as an oxygen evolution reaction anode material, a test was conducted in a 0.5 mol / L sulfuric acid solution, and the polarization curve and stability curve obtained from the test are shown in FIGS. 42 and 43. As shown in FIG. 42, curve A is the polarization curve of the oxygen evolution reaction of the niobium-doped ruthenium oxide nanomaterial obtained in Comparative Example 2, and curve B is the polarization curve of the oxygen evolution reaction of the niobium-doped ruthenium oxide nanomaterial obtained in Example 1. From FIG. 42, at 10 mA / cm 2 , it was found that the overpotential of the niobium-doped ruthenium oxide obtained in Example 1 was 196 mV, while the overpotential of the niobium-doped ruthenium oxide obtained in Comparative Example 2 was 228 mV. Therefore, the niobium-doped ruthenium oxide obtained with the polymer multi-dentate ligand had higher oxygen evolution reaction activity. FIG. 43 is the stability curve of the niobium-doped ruthenium oxide obtained in Comparative Example 2 at a current density of 100 mA / cm 2 . From FIG. 43, it was found that after 80 hours, a decay of 100 mV or more was observed in the stability curve. In FIG. 43, compared with FIG. 21, it was confirmed that the stability of the oxygen evolution reaction of the niobium-doped ruthenium oxide nanomaterial obtained using citric acid as a ligand was inferior to that of the niobium-doped ruthenium oxide nanomaterial obtained using polyvinylpyrrolidone. Therefore, the difference in stability between the niobium-doped ruthenium oxide nanomaterial of Comparative Example 2 and the niobium-doped ruthenium oxide obtained in Example 1 was significant. It was further confirmed that the stability of the oxygen evolution reaction of the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial produced with the polymer multi-dentate ligand was very excellent. In each of the following experiments, the oxygen evolution activity of the transition metal-doped ruthenium oxide nanomaterial of the present invention in water electrolysis was tested by a three-electrode system, and a polarization curve was obtained. In the three-electrode system, a calomel electrode was used as the reference electrode, a platinum sheet electrode was used as the counter electrode, and the transition metal-doped ruthenium oxide nanomaterial obtained in the examples was used as the working electrode. When it was necessary to make a comparison, the following specific other materials were used as the working electrode for comparison. In each of the following experiments, the stability of oxygen evolution of the transition metal-doped ruthenium oxide nanomaterial of the present invention in water electrolysis was tested by a two-electrode system, and a stability curve was obtained. In the two-electrode system, a platinum sheet electrode was used as the cathode, and the transition metal-doped ruthenium oxide nanomaterial obtained in the examples was used as the anode. When it was necessary to make a comparison, the following specific other materials were used as the working electrode for comparison. Example 21 - Hydrothermal treatment method

[0124] The method for manufacturing the manganese-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a potassium permanganate solution and a manganese chloride tetrahydrate solution that had been ultrasonically treated uniformly were added in sequence so that divalent manganese ions were present in a sufficiently oxidized liquid environment. When the addition of all the reaction solutions was completed, it was stirred sufficiently for 0.5 h. The concentration of ruthenium chloride in the beaker was controlled to 0.4 mol / L, and the concentration of manganese chloride was controlled to 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to 50 g / L, and it was stirred for another 1 h to obtain a uniformly colored manganese-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment autoclave, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment autoclave and naturally cooling it to room temperature, the reaction solution in the autoclave was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C to bake to obtain a uniformly colored metal powder precursor. (2) Put the metal powder precursor obtained in step (1) into a boat, and then put the boat containing the metal powder precursor into a muffle furnace. Set the heating rate to 10 °C / min, heat it up to 400 °C, keep it at this temperature for 3 h, then cool it naturally to obtain the manganese-doped ruthenium oxide nanomaterial with a manganese doping amount of 20%. The calculation formula for the manganese doping amount is N manganese / (N manganese + N ruthenium) = 0.1 / 0.5 = 20%. Characterization of Manganese-Doped Ruthenium Oxide Nanomaterials The scanning electron microscope image of the obtained manganese-doped ruthenium oxide nanomaterial is shown in Figure 44, and its XRD spectrum is shown in Figure 45. From Figure 44, it can be seen that the manganese-doped ruthenium oxide nanomaterial is spherical particles with a size of 70 - 200 nm, and its surface is rough. The XRD spectrum of the obtained manganese-doped ruthenium oxide nanomaterial is shown in Figure 45. From Figure 45, it can be seen that the manganese-doped ruthenium oxide nanomaterial shows characteristic peaks of rutile-phase ruthenium oxide. Compared with the standard card of rutile-phase ruthenium oxide, the diffraction peaks of manganese-doped ruthenium oxide shift to a larger angle, and no diffraction peaks of manganese oxide are found. This indicates that the manganese element is well doped into the crystal of ruthenium oxide, for example, and no phase separation occurs. That is, the manganese in the manganese-doped ruthenium oxide nanomaterial is doped into the interior of the ruthenium oxide crystal and replaces part of the positions of ruthenium in the lattice. Therefore, from Figure 45, the molecular formula of the material is Mn x Ru 1-x O 2 It was confirmed that it is. The element distribution diagram of the obtained manganese-doped ruthenium oxide nanomaterial is shown in Figure 46. From Figure 46, it can be seen that the elements of the manganese-doped ruthenium oxide nanomaterial are uniformly distributed. This confirms that manganese is uniformly dispersed in the interior of the ruthenium oxide crystal. Therefore, both manganese and ruthenium in the manganese-doped ruthenium oxide nanomaterial are uniformly dispersed. Example 22 - Hydrothermal Treatment Method

[0125] Referring to the method of Example 21, polyvinylpyrrolidone was changed to polyvinyl alcohol. In the beaker, the concentration of ruthenium chloride solution was controlled to 1 mol / L, the solubility of manganese chloride solution was controlled to 0.01 mol / L, and the concentration of polyvinyl alcohol in the beaker was controlled to 50 g / L. As for the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 1%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 0.01 / (1 + 0.01) = 1%. Example 23 - Hydrothermal treatment method

[0126] Referring to the method of Example 21, polyvinylpyrrolidone was changed to ethylenediamine. In the beaker, the concentration of ruthenium chloride solution was controlled to 1 mol / L, the solubility of manganese chloride solution was controlled to 1 mol / L, and the concentration of ethylenediamine in the beaker was controlled to 50 g / L. As for the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 50%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 1 / (1 + 1) = 50%. Example 24 - Hydrothermal treatment method

[0127] Referring to the method of Example 21, in the beaker, the concentration of ruthenium chloride solution was controlled to 0.4 mol / L, the solubility of manganese chloride solution was controlled to 0.1 mol / L, and the concentration of polyvinylpyrrolidone in the beaker was controlled to 1 g / L. As for the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 0.1 / (0.4 + 0.1) = 20%. Example 25 - Hydrothermal treatment method

[0128] Referring to the method of Example 1, polyvinylpyrrolidone was changed to polylactic acid. In the beaker, the concentration of ruthenium chloride solution was controlled at 0.4 mol / L, the solubility of manganese chloride solution was controlled at 0.1 mol / L, and the concentration of polylactic acid in the beaker was controlled at 1 g / L. As the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the holding temperature was 400 °C, and the holding time was 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 0.1 / (0.4 + 0.1) = 20%. Comparative Example 3 - Hydrothermal treatment method

[0129] Those skilled in the art may consider that the presence of the ligand promotes the doping of transition metal manganese into the ruthenium oxide lattice and improves the stability of the catalyst. In this comparative example, the following experiment was conducted using ammonium citrate as the ligand. Referring to the manufacturing method of Example 21, compared with Example 21, ammonium citrate was used instead of polyvinylpyrrolidone with multiple coordination sites, that is, before transferring the reaction solution to the hydrothermal treatment kettle, ammonium citrate was added thereto, and the concentration of ammonium citrate was controlled at 50 g / L. Next, ammonia water was added to adjust the pH to neutral. While stirring, the ammonium citrate solution was mixed with the reaction solution and stirred well to obtain the manganese-doped ruthenium oxide nanomaterial with a manganese doping amount of 20%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 0.1 / 0.5 = 20%. Comparative Example 4 - Hydrothermal treatment method

[0130] In this comparative example, the following experiments were conducted using manganese chloride tetrahydrate and potassium permanganate as examples. Referring to the manufacturing method of Example 21, compared with Example 21, without adding multi-coordination site polyvinylpyrrolidone, it was sufficiently stirred and reacted to obtain the manganese-doped ruthenium oxide nanomaterial with a manganese doping amount of 20%. The calculation formula for the manganese doping amount is N manganese / (N manganese + N ruthenium) = 1 / 5 = 20%. Example 26 - Hydrothermal treatment method

[0131] The manufacturing method of the chromium-doped ruthenium oxide nanomaterial includes the following steps. (1) Put an aqueous solution of ruthenium chloride into a beaker, and then sequentially add a potassium dichromate solution and a chromium chloride solution that have been uniformly ultrasonicated so that trivalent chromium ions exist in a sufficiently oxidized liquid environment. After the addition of all the reaction solutions was completed, it was sufficiently stirred for 0.5 h. The concentration of ruthenium chloride in the beaker was controlled to be 0.4 mol / L, and the concentration of chromium chloride was controlled to be 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to be 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored chromium-ruthenium oxide solution. Next, transfer the reaction solution in the beaker to a hydrothermal treatment kettle, put it into a forced-air oven, and keep it at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then put into an oven at 80 °C to bake to obtain a uniformly colored metal powder precursor. (2) Put the metal powder precursor obtained in step (1) into a boat, and then put the boat containing the metal powder precursor into a muffle furnace. Set the heating rate to 10 °C / min, heat it up to 400 °C, keep it warm for 3 h, and then naturally cool it to obtain the chromium-doped ruthenium oxide nanomaterial with a chromium doping amount of 20%. The calculation formula for the chromium doping amount is N chromium / (N chromium + N ruthenium) = 0.1 / 0.5 = 20%. Characteristic evaluation of the chromium-doped ruthenium oxide nanomaterial The scanning electron microscope image of the obtained chromium-doped ruthenium oxide nanomaterial is shown in Figure 47, and its XRD spectrum is shown in Figure 48. From Figure 47, it was found that the chromium-doped ruthenium oxide nanomaterial is spherical particles with a size of 70 - 200 nm and a rough surface. The XRD spectrum of the obtained chromium-doped ruthenium oxide nanomaterial is shown in Figure 48. From Figure 48, the chromium-doped ruthenium oxide nanomaterial shows characteristic peaks of rutile-phase ruthenium oxide. Compared with the standard card of rutile-phase ruthenium oxide, it was found that the diffraction peaks of chromium-doped ruthenium oxide shifted to a larger angle and there were no diffraction peaks of chromium oxide. From this, it was clarified that the chromium element was successfully doped into the ruthenium oxide crystal without phase separation. That is, in the said chromium-doped ruthenium oxide nanomaterial, chromium is doped into the interior of the ruthenium oxide crystal and replaces part of the position of ruthenium in the lattice. Therefore, from Figure 48, the molecular formula of the material was confirmed to be Cr x Ru 1-x O 2 The element distribution diagram of the obtained chromium-doped ruthenium oxide nanomaterial is shown in Figure 49. From Figure 49, it was revealed that the elements of the chromium-doped ruthenium oxide nanomaterial are uniformly distributed. From this, it was confirmed that chromium is uniformly dispersed inside the ruthenium oxide crystal. Therefore, both chromium and ruthenium in the said chromium-doped ruthenium oxide nanomaterial are uniformly dispersed. Comparative Example 5 - Hydrothermal Treatment Method

[0132] Those skilled in the art may consider that the presence of the ligand promotes the doping of transition metal chromium into the ruthenium oxide crystal and improves the stability of the catalyst. In this comparative example, the following experiment was conducted using ammonium citrate as the ligand as an example. ​Referring to the manufacturing method of Example 26, compared with Example 26, ammonium citrate was used instead of multi-ligand polyvinylpyrrolidone. That is, before transferring the reaction solution to the hydrothermal treatment kettle, ammonium citrate was added thereto, and the concentration of ammonium citrate was controlled to 50 g / L, which is different. Next, ammonia water was added to adjust the pH to neutral. While stirring, the ammonium citrate solution was mixed with the reaction solution and stirred well to obtain the chromium-doped ruthenium oxide nanomaterial with a chromium doping amount of 20%. The calculation formula for the chromium doping amount is N chromium / (N chromium + N ruthenium) = 1 / 5 = 20%. Comparative Example 6 - Hydrothermal treatment method

[0133] In this comparative example, the following experiments were carried out using chromium chloride and potassium dichromate as examples. Referring to the manufacturing method of Example 26, compared with Example 26, without adding multi-ligand polyvinylpyrrolidone, it was stirred well and reacted to obtain the chromium-doped ruthenium oxide nanomaterial with a chromium doping amount of 20%, which is different. The calculation formula for the chromium doping amount is N chromium / (N chromium + N ruthenium) = 1 / 5 = 20%. Example 27 - Hydrothermal treatment method

[0134] The manufacturing method of the tin-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated tin tetrachloride pentahydrate solution was added. After the addition of all the reaction solution was completed, the beaker was ultrasonically treated for 1 h sufficiently. The concentration of ruthenium chloride in the beaker was controlled to 0.4 mol / L, and the concentration of tin chloride was controlled to 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to 50 g / L, and it was stirred for another 1 h to obtain a uniformly colored tin-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C to bake, obtaining a metal powder precursor with a uniform color. (2) The metal powder precursor obtained in step (1) was put into a boat, and then the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set at 10 °C / min, heated to 400 °C, kept warm for 3 h, and then naturally cooled to obtain the tin-doped ruthenium oxide nanomaterial with a tin doping amount of 20%. The calculation formula for the tin doping amount is Ntin / (Ntin + Nruthenium)=0.1 / 0.5 = 20%. Characterization of the tin-doped ruthenium oxide nanomaterial The scanning electron microscope image of the obtained tin-doped ruthenium oxide nanomaterial is shown in Fig. 50, and its XRD spectrum is shown in Fig. 51. From Fig. 51, it was found that the tin-doped ruthenium oxide nanomaterial is spherical particles with a size of 70 - 200 nm and its surface is rough. From Fig. 51, the tin-doped ruthenium oxide nanomaterial shows characteristic peaks of rutile-phase ruthenium oxide. Compared with the standard card of rutile-phase ruthenium oxide, it was found that the diffraction peaks of tin-doped ruthenium oxide shifted to a larger angle and there were no diffraction peaks of tin oxide. From this, it was revealed that tin elements were successfully doped into the ruthenium oxide crystal without phase separation. That is, in the tin-doped ruthenium oxide nanomaterial, tin is doped into the interior of the ruthenium oxide crystal, substituting part of the position of ruthenium in the lattice. Therefore, from Fig. 51, the molecular formula of the material is Sn x Ru 1-x O 2 It was confirmed that it is. The elemental distribution diagram of the obtained tin-doped ruthenium oxide nanomaterial is shown in Fig. 52. From Fig. 52, it was found that the elements of the tin-doped ruthenium oxide nanomaterial are uniformly distributed. From this, it was confirmed that tin is uniformly dispersed inside the ruthenium oxide crystal. Therefore, both tin and ruthenium in the tin-doped ruthenium oxide nanomaterial are uniformly dispersed. Comparative Example 7 - Hydrothermal treatment method

[0135] Those skilled in the art may consider that the presence of the ligand promotes the doping of transition metal tin into the ruthenium oxide crystal and improves the stability of the catalyst. In this comparative example, the following experiment was conducted using ammonium citrate as the ligand. Referring to the manufacturing method of Example 27, compared with Example 27, ammonium citrate was used instead of multi-ligand polyvinylpyrrolidone. That is, before transferring the reaction solution to the hydrothermal treatment kettle, ammonium citrate was added thereto, and the concentration of ammonium citrate was controlled to 50 g / L. Next, ammonia water was added to adjust the pH to neutral. While stirring, the ammonium citrate solution was mixed with the reaction solution and stirred well to obtain a tin-doped ruthenium oxide nanomaterial with a tin doping amount of 20%. The calculation formula for the tin doping amount is Ntin / (Ntin + Nruthenium) = 1 / 5 = 20%. Comparative Example 8 - Hydrothermal treatment method

[0136] In this comparative example, the following experiment was conducted using tin(IV) chloride pentahydrate as an example. Referring to the manufacturing method of Example 27, compared with Example 27, without adding multi-ligand polyvinylpyrrolidone, it was stirred well and reacted to obtain a tin-doped ruthenium oxide nanomaterial with a tin doping amount of 20%. The calculation formula for the tin doping amount is Ntin / (Ntin + Nruthenium) = 1 / 5 = 20%. Example 28 - Germanium-doped ruthenium oxide

[0137] The manufacturing method of the germanium-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated germanium tetrachloride solution was added. After the addition of all the reaction solutions was completed, it was mechanically stirred for 1 h. The concentration of ruthenium chloride in the beaker was controlled to be 0.4 mol / L, and the concentration of germanium chloride was controlled to be 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to be 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored germanium-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was alternately centrifuged with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C to bake to obtain a uniformly colored metal powder precursor. (2) The metal powder precursor obtained in step (1) was placed in a boat, and then the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set to 10 °C / min, heated to 400 °C, kept warm for 3 h, and then naturally cooled to obtain the germanium-doped ruthenium oxide nanomaterial with a germanium doping amount of 20%. The calculation formula for the germanium doping amount is N germanium / (N germanium + N ruthenium) = 0.1 / 0.5 = 20%. Example 29 - Indium-doped ruthenium oxide The manufacturing method of the indium-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated indium chloride solution was added. After the addition of all the reaction solutions was completed, it was mechanically stirred for 0.5 h. The concentration of ruthenium chloride in the beaker was controlled to be 0.4 mol / L, and the concentration of indium chloride was controlled to be 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to be 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored indium-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C to bake, obtaining a metal powder precursor with a uniform color. (2) The metal powder precursor obtained in step (1) was placed in a boat, and then the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set to 10 °C / min, and the temperature was raised to 400 °C and kept at this temperature for 3 h, followed by natural cooling, obtaining the indium-doped ruthenium oxide nanomaterial with an indium doping amount of 20%. The calculation formula for the indium doping amount is N indium / (N indium + N ruthenium) = 0.1 / (0.1 + 0.4) = 20%. Example 30 - Antimony-doped ruthenium oxide

[0138] The manufacturing method of the antimony-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated antimony trichloride solution was added. When the addition of all the reaction solutions was completed, the beaker was ultrasonically treated for 1 h. The concentration of ruthenium chloride in the beaker was controlled to be 0.4 mol / L, and the concentration of antimony trichloride was controlled to be 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to be 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored antimony-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C to bake, obtaining a metal powder precursor with a uniform color. (2) Put the metal powder precursor obtained in step (1) into a boat. Then, place the boat containing the metal powder precursor into a muffle furnace, set the heating rate to 10 °C / min, heat it up to 400 °C, keep it at this temperature for 3 h, then cool it naturally to obtain the antimony-doped ruthenium oxide nanomaterial with an antimony doping amount of 20%. The calculation formula for the antimony doping amount is N antimony / (N antimony + N ruthenium) = 0.1 / (0.1 + 0.4) = 20%. Example 31 - Niobium-doped ruthenium oxide

[0139] The manufacturing method of the niobium-doped ruthenium oxide nanomaterial includes the following steps. (1) Put an aqueous solution of ruthenium chloride into a beaker, and then add a niobium pentachloride solution that has been uniformly ultrasonicated. After the addition of all the reaction solutions is completed, ultrasonicate the beaker thoroughly for 1 h. Control the concentration of ruthenium chloride in the beaker to 0.4 mol / L and the concentration of niobium chloride to 0.1 mol / L. Next, add polyvinylpyrrolidone powder to the solution, control the concentration of polyvinylpyrrolidone in the beaker to 50 g / L, and stir for another 1 h to obtain a uniformly colored niobium-ruthenium oxide solution. Next, transfer the reaction solution in the beaker to a hydrothermal treatment kettle, place it in a forced-air oven, and keep it at 180 °C for 10 h. Take out the hydrothermal treatment kettle and let it cool naturally to room temperature. Then, centrifuge the reaction solution in the kettle alternately with deionized water and absolute ethanol, wash it multiple times, and then put it into an oven at 80 °C to bake to obtain a uniformly colored metal powder precursor. (2) Put the metal powder precursor obtained in step (1) into a boat. Then, place the boat containing the metal powder precursor into a muffle furnace, set the heating rate to 10 °C / min, heat it up to 400 °C, keep it at this temperature for 3 h, then cool it naturally to obtain the niobium-doped ruthenium oxide nanomaterial with a niobium doping amount of 20%. The calculation formula for the niobium doping amount is N niobium / (N niobium + N ruthenium) = 0.1 / (0.1 + 0.4) = 20%. Example 32 - Titanium-doped ruthenium oxide

[0140] The manufacturing method of the titanium-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated titanium chloride solution was added. After all the reaction solution was added, the beaker was ultrasonically treated sufficiently for 1 h. The concentration of ruthenium chloride in the beaker was controlled to 0.4 mol / L, and the concentration of titanium chloride was controlled to 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored titanium-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C and baked to obtain a uniformly colored metal powder precursor. (2) The metal powder precursor obtained in step (1) was placed in a boat, and then the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set to 10 °C / min, heated to 400 °C, kept warm for 3 h, and then naturally cooled to obtain the titanium-doped ruthenium oxide nanomaterial with a titanium doping amount of 20%. The calculation formula for the titanium doping amount is N titanium / (N titanium + N ruthenium) = 0.1 / (0.1 + 0.4) = 20%. Example 33 - Zirconium-doped ruthenium oxide

[0141] The manufacturing method of the zirconium-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated zirconium chloride solution was added. After all the reaction solution was added, the beaker was ultrasonically treated sufficiently for 1 h. The concentration of ruthenium chloride in the beaker was controlled to 0.4 mol / L, and the concentration of zirconium chloride was controlled to 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored zirconium-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was alternately centrifuged with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C for baking to obtain a metal powder precursor with a uniform color. (2) The metal powder precursor obtained in step (1) was put into a boat, and then the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set at 10 °C / min, heated to 400 °C, kept warm for 3 h, and then naturally cooled to obtain the zirconium-doped ruthenium oxide nanomaterial with a zirconium doping amount of 20%. The calculation formula for the zirconium doping amount is Nzirconium / (Nzirconium + Nruthenium)=0.1 / (0.1 + 0.4)=20%. Example 34 - Hafnium-doped ruthenium oxide

[0142] The manufacturing method of the hafnium-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was put into a beaker, and then a hafnium oxide solution uniformly treated with ultrasonic waves was added. After all the reaction solutions were added, mechanical stirring was carried out for 0.5 h. The concentration of ruthenium chloride in the beaker was controlled to be 0.4 mol / L, and the concentration of hafnium oxide was controlled to be 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to be 50 g / L, and stirring was carried out for another 1 h to obtain a hafnium-ruthenium oxide solution with a uniform color. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was alternately centrifuged with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C for baking to obtain a metal powder precursor with a uniform color. (2) Put the metal powder precursor obtained in step (1) into a boat. Then, place the boat containing the metal powder precursor into a muffle furnace, set the heating rate to 10 °C / min, heat it up to 400 °C, keep it at this temperature for 3 h, and then let it cool naturally to obtain the hafnium-doped ruthenium oxide nanomaterial with a hafnium doping amount of 20%. The calculation formula for the hafnium doping amount is N hafnium / (N hafnium + N ruthenium) = 0.1 / (0.1 + 0.4) = 20%. Example 35 - Tungsten-doped ruthenium oxide

[0143] The manufacturing method of the tungsten-doped ruthenium oxide nanomaterial includes the following steps. (1) Put an aqueous solution of ruthenium chloride into a beaker, and then add a uniformly ultrasonicated tungsten oxide solution. After the addition of all the reaction solutions is completed, ultrasonically treat the beaker for 1 h. Control the concentration of ruthenium chloride in the beaker to 0.4 mol / L and the concentration of tungsten oxide to 0.1 mol / L. Next, add polyvinylpyrrolidone powder to the solution, control the concentration of polyvinylpyrrolidone in the beaker to 50 g / L, and stir for another 1 h to obtain a tungsten-ruthenium oxide solution of uniform color. Next, transfer the reaction solution in the beaker to a hydrothermal treatment kettle, place it in a forced-air oven, and keep it at 180 °C for 10 h. Take out the hydrothermal treatment kettle, let it cool naturally to room temperature, then centrifuge the reaction solution in the kettle alternately with deionized water and absolute ethanol, wash it multiple times, and then put it into an oven at 80 °C to bake to obtain a metal powder precursor of uniform color. (2) Put the metal powder precursor obtained in step (1) into a boat. Then, place the boat containing the metal powder precursor into a muffle furnace, set the heating rate to 10 °C / min, heat it up to 400 °C, keep it at this temperature for 3 h, and then let it cool naturally to obtain the tungsten-doped ruthenium oxide nanomaterial with a tungsten doping amount of 20%. The calculation formula for the tungsten doping amount is N tungsten / (N tungsten + N ruthenium) = 20%. Example 36 - Molybdenum-doped ruthenium oxide

[0144] The manufacturing method of molybdenum-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated molybdenum chloride solution was added. After the addition of all the reaction solutions was completed, the beaker was ultrasonically treated sufficiently for 1 h. The concentration of ruthenium chloride in the beaker was controlled to be 0.4 mol / L, and the concentration of molybdenum chloride was controlled to be 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to be 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored molybdenum-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept warm at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C for baking to obtain a uniformly colored metal powder precursor. (2) The metal powder precursor obtained in step (1) was placed in a boat, and then the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set to 10 °C / min, heated to 400 °C, kept warm for 3 h, and then naturally cooled to obtain the molybdenum-doped ruthenium oxide nanomaterial with a molybdenum doping amount of 20%. The calculation formula for the molybdenum doping amount is N molybdenum / (N molybdenum + N ruthenium) = 20%. Example 37 - Tantalum-doped ruthenium oxide

[0145] The manufacturing method of tantalum-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was placed in a beaker, and then a uniformly ultrasonicated tantalum pentachloride solution was added. After the addition of all the reaction solutions was completed, the beaker was ultrasonically treated sufficiently for 1 h. The concentration of ruthenium chloride in the beaker was controlled to be 0.4 mol / L, and the concentration of tantalum chloride was controlled to be 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled to be 50 g / L, and it was further stirred for 1 h to obtain a uniformly colored tantalum-ruthenium oxide solution. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C for baking to obtain a metal powder precursor with a uniform color. (2) The metal powder precursor obtained in step (1) was put into a boat, and then the boat containing the metal powder precursor was placed in a muffle furnace. The heating rate was set at 10 °C / min, and the temperature was raised to 400 °C and kept for 3 h, followed by natural cooling to obtain the tantalum-doped ruthenium oxide nanomaterial with a tantalum doping amount of 20%. The calculation formula for the tantalum doping amount is N tantalum / (N tantalum + N ruthenium) = 20%. Example 38 - Platinum-doped ruthenium oxide

[0146] The manufacturing method of the platinum-doped ruthenium oxide nanomaterial includes the following steps. (1) An aqueous solution of ruthenium chloride was put into a beaker, and then a chloroplatinic acid solution uniformly treated by ultrasonic waves was added. After the addition of all the reaction solutions was completed, the beaker was ultrasonically treated sufficiently for 1 h. The concentration of ruthenium chloride in the beaker was controlled at 0.4 mol / L, and the concentration of chloroplatinic acid was controlled at 0.1 mol / L. Next, polyvinylpyrrolidone powder was added to the solution, and the concentration of polyvinylpyrrolidone in the beaker was controlled at 50 g / L, and it was further stirred for 1 h to obtain a platinum-ruthenium oxide solution with a uniform color. Next, the reaction solution in the beaker was transferred to a hydrothermal treatment kettle, placed in a forced-air oven, and kept at 180 °C for 10 h. After taking out the hydrothermal treatment kettle and naturally cooling it to room temperature, the reaction solution in the kettle was centrifuged alternately with deionized water and absolute ethanol, washed multiple times, and then placed in an oven at 80 °C for baking to obtain a metal powder precursor with a uniform color. (2) Put the metal powder precursor obtained in step (1) into a boat, and then put the boat containing the metal powder precursor into a muffle furnace. Set the heating rate to 10 °C / min, heat it up to 400 °C, keep it warm for 3 h, then cool it naturally to obtain the tantalum-doped ruthenium oxide nanomaterial with a platinum doping amount of 20%. The calculation formula for the platinum doping amount is N platinum / (N platinum + N ruthenium) = 20%. Example 39 - Manganese-doped ruthenium oxide

[0147] Referring to the method of Example 21, control the concentration of ruthenium chloride solution in a beaker to 0.4 mol / L, the solubility of manganese chloride solution to 0.1 mol / L, and control the concentration of polyvinylpyrrolidone in the beaker to 50 g / L. As the reaction conditions of the oven, the heat preservation temperature is 100 °C and the heat preservation time is 4 h. As the roasting conditions of the muffle furnace, the heating rate is 10 °C / min, the heat preservation temperature is 400 °C, and the heat preservation time is 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the manganese doping amount is N manganese / (N manganese + N ruthenium) = 20%. Example 40 - Manganese-doped ruthenium oxide

[0148] Referring to the method of Example 21, control the concentration of ruthenium chloride solution in a beaker to 0.4 mol / L, the solubility of manganese chloride solution to 0.1 mol / L, and control the concentration of polyvinylpyrrolidone in the beaker to 50 g / L. As the reaction conditions of the oven, the heat preservation temperature is 180 °C and the heat preservation time is 4 h. As the roasting conditions of the muffle furnace, the heating rate is 10 °C / min, the heat preservation temperature is 400 °C, and the heat preservation time is 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the manganese doping amount is N manganese / (N manganese + N ruthenium) = 20%. Example 41 - Manganese-doped ruthenium oxide

[0149] Referring to the method of Example 21, the concentration of ruthenium chloride solution in the beaker was controlled at 0.4 mol / L, the solubility of manganese chloride solution was controlled at 0.1 mol / L, and the concentration of polyvinylpyrrolidone in the beaker was controlled at 50 g / L. As for the reaction conditions of the oven, the heat preservation temperature was 100 °C and the heat preservation time was 10 h. As for the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the heat preservation temperature was 400 °C, and the heat preservation time was 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 20%. Example 42 - Manganese-doped Ruthenium Oxide

[0150] Referring to the method of Example 21, the concentration of ruthenium chloride solution in the beaker was controlled at 0.4 mol / L, the solubility of manganese chloride solution was controlled at 0.1 mol / L, and the concentration of polyvinylpyrrolidone in the beaker was controlled at 50 g / L. As for the reaction conditions of the oven, the heat preservation temperature was 180 °C and the heat preservation time was 10 h. As for the roasting conditions of the muffle furnace, the heating rate was 1 °C / min, the heat preservation temperature was 300 °C, and the heat preservation time was 3 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 20%. Example 43 - Manganese-doped Ruthenium Oxide

[0151] Referring to the method of Example 21, the concentration of ruthenium chloride solution in the beaker was controlled at 0.4 mol / L, the solubility of manganese chloride solution was controlled at 0.1 mol / L, and the concentration of polyvinylpyrrolidone in the beaker was controlled at 50 g / L. As for the reaction conditions of the oven, the heat preservation temperature was 180 °C and the heat preservation time was 10 h. As for the roasting conditions of the muffle furnace, the heating rate was 10 °C / min, the heat preservation temperature was 500 °C, and the heat preservation time was 5 h. The doping amount of manganese in the manganese-doped ruthenium oxide nanomaterial is 20%. The calculation formula for the doping amount of manganese is N manganese / (N manganese + N ruthenium) = 20%. Application Example 7 - Activity Test

[0152] Using a calomel electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the manganese-doped ruthenium oxide nanomaterials obtained in Examples 21 to 25 and commercially available ruthenium dioxide as the working electrode, in a three-electrode system, 0.5 mol / L of H 2 SO 4 In the solution, the oxygen evolution characteristics of the manganese-doped ruthenium oxide nanomaterial of the present invention in water electrolysis were tested, and the obtained polarization curves are shown in Fig. 53. From Fig. 53, the manganese-doped ruthenium oxide nanomaterials obtained in Examples 21 to 25 are excellent in oxygen evolution characteristics (curves A - E in Fig. 53) in water electrolysis, and are far superior to the commercially available ruthenium dioxide material (curve F in Fig. 53). The overvoltages at a current density of 10 mA / cm 2 are 170 mV, 300 mV, 250 mV, 190 mV, and 160 mV respectively, and it was found that all are lower than the overvoltage of 320 mV of commercially available ruthenium dioxide. Application Example 8 - Stability Test

[0153] Using a two-electrode system with the manganese-doped ruthenium oxide nanomaterials obtained in Example 21, Example 24, and Example 25 or commercially available ruthenium dioxide as the anode and a platinum sheet electrode as the cathode, the stability of the oxygen evolution reaction in water electrolysis of the manganese-doped ruthenium oxide nanomaterial of the present invention was tested. Fig. 54 shows 0.5 mol / L of H when used as the oxygen evolution anode material of the manganese-doped ruthenium oxide materials obtained in Example 21, Example 24, and Example 25 of the present invention. 2 SO 4 In the solution at 100 mA / cm 2Stability curves at current density. FIG. 55 shows the stability curves at 0.5 mol / L H 2 SO 4 solution when the manganese-doped ruthenium oxide materials obtained in Example 21, Example 24, and Example 25 of the present invention are used as oxygen evolution anode materials at a current density of 200 mA / cm 2 . From FIGS. 54 and 55, when maintained at current densities of 100 and 200 mA / cm 2 for 24 hours and 80 - 100 hours respectively, it was found that the current of the manganese-doped ruthenium oxide nanomaterials obtained in Example 21, Example 24, and Example 25 hardly decayed. As shown in FIG. 81, it was confirmed that the stability of the catalyst material at high current density is much better than that of commercially available ruthenium dioxide. It was revealed that the manganese-doped ruthenium oxide nanomaterials obtained in Example 21, Example 24, and Example 25 have higher stability at high current density when used as oxygen evolution reaction anode materials. Application Example 9 - Activity Test

[0154] Using a calomel electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the manganese-doped ruthenium oxide nanomaterials obtained in Example 21 and Comparative Example 3 and commercially available ruthenium dioxide as the working electrodes, in a three-electrode system, the oxygen evolution characteristics of the manganese-doped ruthenium oxide nanomaterials of the present invention in water electrolysis were tested in a 0.5 mol / L H 2 SO 4 solution, and the obtained polarization curves are shown in FIG. 56. From FIG. 56, the manganese-doped ruthenium oxide nanomaterials obtained in Example 21 and Comparative Example 3 are excellent in oxygen evolution characteristics (curves A and B in FIG. 56) in water electrolysis, and are much better than the commercially available ruthenium dioxide material (curve C in FIG. 56). At a current density of 10 mA / cm 2 , the overvoltages are 170 mV and 220 mV respectively, both of which are lower than the overvoltage of 320 mV of commercially available ruthenium dioxide. Application Example 10 - Stability Test

[0155] The stability of the oxygen evolution reaction in the water electrolysis of the manganese-doped ruthenium oxide nanomaterial of the present invention was tested by a two-electrode system using the manganese-doped ruthenium oxide nanomaterial obtained in Example 21 and Comparative Example 3 as anodes or commercially available ruthenium dioxide, and a platinum sheet electrode as a cathode. Figure 57 shows 0.5 mol / L H 2 SO 4 solution when used as the oxygen evolution anode material of the manganese-doped ruthenium oxide material obtained in Comparative Example 3 of the present invention at a current density of 100 mA / cm 2 is the stability curve, and Figure 58 shows 0.5 mol / L H 2 SO 4 solution when used as the oxygen evolution anode material of the manganese-doped ruthenium oxide material obtained in Comparative Example 3 of the present invention at a current density of 200 mA / cm 2 is the stability curve. From Figures 57 and 58, when maintained at current densities of 100 and 200 mA / cm 2 for 24 hours and 100 hours respectively, it was found that the manganese-doped ruthenium oxide nanomaterial obtained in Comparative Example 3 had a rapid decay of current at a high current density of 200 mA / cm 2 . From this, it was clarified that the manganese-doped ruthenium oxide nanomaterial obtained by adding ammonium citrate was inferior in stability at high current density to the manganese-doped ruthenium oxide nanomaterial obtained in Example 21 when used as the oxygen evolution reaction anode material. Therefore, in this application example, it was recognized that the manganese-doped ruthenium oxide nanomaterial formed by adding a multi-ligand polymer was significantly improved in both activity and stability compared to the manganese-doped ruthenium oxide nanomaterial formed by adding ammonium citrate as a ligand when used as the oxygen evolution reaction anode material. Application Example 11 - Test of Activity and Stability

[0156] Using a calomel electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the manganese-doped ruthenium oxide nanomaterials obtained in Example 21 and Comparative Example 4 and commercially available ruthenium dioxide as the working electrode, in a 3-electrode system, in a 0.5 mol / L H 2 SO 4 solution, the oxygen evolution characteristics of the manganese-doped ruthenium oxide nanomaterial of the present invention in water electrolysis were tested, and the obtained polarization curves are shown in Fig. 59. Using the manganese-doped ruthenium oxide nanomaterials obtained in Example 21 and Comparative Example 4 or commercially available ruthenium dioxide as the anode and a platinum sheet electrode as the cathode, the stability of the oxygen evolution reaction in the water electrolysis of the manganese-doped ruthenium oxide nanomaterial of the present invention was tested by a 2-electrode system. From Fig. 59, the manganese-doped ruthenium oxide nanomaterials obtained in Example 21 and Comparative Example 4 are excellent in oxygen evolution characteristics (curve B and curve A in Fig. 59) in water electrolysis, far superior to the commercially available ruthenium dioxide material (curve C in Fig. 59), and the overpotentials are 170 mV and 190 mV respectively at a current density of 10 mA / cm 2 It was found that both are lower than 320 mV of commercially available ruthenium dioxide. The manganese-doped ruthenium oxide nanomaterial obtained in Example 21 is more active than the manganese-doped ruthenium oxide nanomaterial obtained in Comparative Example 4 when used as the electrode catalyst of the oxygen evolution reaction anode material. Fig. 60 is the stability curve at a current density of 50 mA / cm 2 SO 4 in a solution when the manganese-doped ruthenium oxide material obtained in Comparative Example 4 of the present invention is used as the oxygen evolution anode material. From Fig. 60, at 50 mA / cm 2 current density 2When maintained at a current density for half an hour, a rapid decay was observed within 400 seconds in the stability curve of the manganese-doped ruthenium oxide nanomaterial obtained in Comparative Example 4. That is, it was found that the stability of the catalyst material at a low current density was very poor. From this, it became clear that when the manganese-doped ruthenium oxide nanomaterial obtained in Comparative Example 4 was used as an oxygen evolution reaction anode material, its stability at a high current density was much lower than that of the manganese-doped ruthenium oxide nanomaterial obtained in Example 21. It was confirmed that the material produced without adding polyvinylpyrrolidone of the multi-coordination polymer significantly decreased both the activity and stability of the electrode catalyst compared with Example 21. Therefore, in this application example, when the manganese-doped ruthenium oxide nanomaterial formed by adding a multi-coordination polymer was used as an oxygen evolution reaction anode material, it was found that both the electrochemical activity and stability were clearly improved compared with the manganese-doped ruthenium oxide nanomaterial formed without adding the multi-coordination polymer. Application Example 12 - Activity Test

[0157] Using a calomel electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the chromium-doped ruthenium oxide nanomaterials obtained in Example 26 and Comparative Example 5 and commercially available ruthenium dioxide as the working electrode, a three-electrode system was used for testing. In a 0.5 mol / L H 2 SO 4 solution, the oxygen evolution characteristics of the chromium-doped ruthenium oxide nanomaterial of the present invention in water electrolysis were tested, and the obtained polarization curve is shown in Fig. 61. From Fig. 61, it was found that both the chromium-doped ruthenium oxide nanomaterials produced in Example 26 and Comparative Example 5 had an overvoltage of 180 mV at 10 mA / cm 2 in the oxygen evolution reaction (curves A and B in Fig. 61), which was much better than the overvoltage of 320 mV of the commercially available ruthenium dioxide material (curve C in Fig. 61). In Example 26, the electrochemical activity corresponded to the nanomaterial obtained in Comparative Example 5. Application Example 13 - Stability Test

[0158] The stability of the oxygen evolution reaction in the water electrolysis of the chromium-doped ruthenium oxide nanomaterial of the present invention was tested by a two-electrode system using the chromium-doped ruthenium oxide nanomaterials obtained in Example 26 and Comparative Example 5 as anodes or commercially available ruthenium dioxide, and a platinum sheet electrode as a cathode. Figure 62 shows 0.5 mol / L H 2 SO 4 solution when used as the oxygen evolution anode material of the chromium-doped ruthenium oxide material obtained in Example 26 of the present invention at a current density of 100 mA / cm 2 and Figure 63 shows 0.5 mol / L H 2 SO 4 solution when used as the oxygen evolution anode material of the chromium-doped ruthenium oxide material obtained in Example 26 of the present invention at a current density of 200 mA / cm 2 The stability curves are shown. From Figures 62 and 63, it was found that when maintained at current densities of 100 and 200 mA / cm 2 for 24 hours and 100 hours respectively, the current of the chromium-doped ruthenium oxide nanomaterial obtained in Example 26 hardly decayed. As shown in Figure 81, the stability of the catalyst material at high current densities is clearly superior to that of commercially available ruthenium dioxide. From this, it was clarified that the chromium-doped ruthenium oxide nanomaterial obtained in Example 26 has high stability at high current densities when used as the oxygen evolution reaction anode material. Figure 64 shows 0.5 mol / L H 2 SO 4 solution when used as the oxygen evolution anode material of the chromium-doped ruthenium oxide material obtained in Comparative Example 5 of the present invention at a current density of 100 mA / cm 2 and Figure 65 shows 0.5 mol / L H 2 SO 4 solution when used as the oxygen evolution anode material of the chromium-doped ruthenium oxide material obtained in Comparative Example 5 of the present invention at a current density of 200 mA / cm 2 The stability curves are shown. From Figures 64 and 65, at 100 and 200 mA / cm2 When maintained for 24 hours and 100 hours respectively at the current density of, the chromium-doped ruthenium oxide nanomaterial obtained in Comparative Example 5 was 200 mA / cm 2 At high current density, it was found that the current decayed rapidly. From this, it became clear that the chromium-doped ruthenium oxide nanomaterial obtained by adding ammonium citrate was inferior in stability at high current density to the chromium-doped ruthenium oxide nanomaterial obtained in Example 26 when used as an oxygen evolution reaction anode material. Therefore, in this application example, it was confirmed that the chromium-doped ruthenium oxide nanomaterial formed by adding a multi-ligand polymer showed significantly improved stability compared to the chromium-doped ruthenium oxide nanomaterial formed by adding ammonium citrate as a complex when used as an oxygen evolution reaction anode material. Application Example 14 - Tests of Activity and Stability

[0159] Using a calomel electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the chromium-doped ruthenium oxide nanomaterials obtained in Example 26 and Comparative Example 6 and commercially available ruthenium dioxide as the working electrode, in a 3-electrode system, in a 0.5 mol / L H 2 SO 4 solution, the oxygen evolution characteristics of the chromium-doped ruthenium oxide nanomaterial of the present invention in water electrolysis were tested, and the obtained polarization curves are shown in Fig. 66. Using a 2-electrode system with the chromium-doped ruthenium oxide nanomaterials obtained in Example 26 and Comparative Example 6 or commercially available ruthenium dioxide as the anode and a platinum sheet electrode as the cathode, the stability of the oxygen evolution reaction of the chromium-doped ruthenium oxide nanomaterial of the present invention in water electrolysis was tested. From Fig. 66, the chromium-doped ruthenium oxide nanomaterials obtained in Example 26 and Comparative Example 6 were excellent in oxygen evolution characteristics (curve B and curve A in Fig. 66) in water electrolysis, and were much superior to the commercially available ruthenium dioxide material (curve C in Fig. 66), and at 10 mA / cm 2It was found that the overvoltage was 170 mV at the current density, both of which were lower than the overvoltage of 320 mV of commercially available ruthenium dioxide. The chromium-doped ruthenium oxide nanomaterial obtained in Example 26 has an activity equivalent to that of the chromium-doped ruthenium oxide nanomaterial obtained in Comparative Example 6 when used as an electrode catalyst for an oxygen evolution reaction anode material. Figure 67 shows 0.5 mol / L H when the chromium-doped ruthenium oxide material obtained in Comparative Example 6 of the present invention is used as an oxygen evolution anode material. 2 SO 4 in the solution at a current density of 50 mA / cm 2 This is a stability curve at the current density. From Figure 67, when maintained at a current density of 50 mA / cm 2 for half an hour, the chromium-doped ruthenium oxide nanomaterial obtained in Comparative Example 6 was found to have a rapid decay within 80 seconds in its stability curve, that is, it was found that the stability of the catalyst material at a low current density was very poor. From this, it became clear that the chromium-doped ruthenium oxide nanomaterial obtained in Comparative Example 6 was much inferior in stability at a high current density to the chromium-doped ruthenium oxide nanomaterial obtained in Example 26 when used as an oxygen evolution reaction anode material. Therefore, in this application example, it was confirmed that the chromium-doped ruthenium oxide nanomaterial formed by adding a multi-ligand polymer has significantly improved stability compared to the manganese-doped ruthenium oxide nanomaterial formed without adding a multi-ligand polymer when used as an oxygen evolution reaction anode material. Application Example 15 - Activity Test

[0160] Using a calomel electrode as a reference electrode, a platinum sheet electrode as a counter electrode, and the tin-doped ruthenium oxide nanomaterials obtained in Example 27 and Comparative Example 7 and commercially available ruthenium dioxide as working electrodes, in a three-electrode system, the oxygen evolution characteristics of the tin-doped ruthenium oxide nanomaterial of the present invention in water electrolysis were tested in a 0.5 mol / L H 2 SO 4 solution, and the obtained polarization curve is shown in Figure 68. From Figure 68, the tin-doped ruthenium oxide nanomaterial obtained in Example 27 is excellent in the oxygen evolution characteristics in water electrolysis (curve A in Figure 68), far superior to the tin-doped ruthenium oxide nanomaterial obtained in Comparative Example 7 (curve B in Figure 68) and the commercially available ruthenium dioxide material (curve C in Figure 68). At a current density of 10 mA / cm 2 It was found that the overpotential is 170 mV, which is significantly lower than the 220 mV of the material obtained in Comparative Example 7 and the 320 mV of the commercially available ruthenium dioxide. From this, it is clear that the nanomaterial of tin-doped ruthenium oxide obtained in Example 27 has more excellent oxygen evolution reaction activity than the nanomaterial of tin-doped ruthenium oxide containing ammonium citrate in Comparative Example 7 and the commercially available ruthenium dioxide. Application Example 16 - Stability Test

[0161] The stability of the oxygen evolution reaction in the water electrolysis of the tin-doped ruthenium oxide nanomaterial of the present invention was tested by a two-electrode system using the tin-doped ruthenium oxide nanomaterial obtained in Example 27 as the anode or the commercially available ruthenium dioxide, and a platinum sheet electrode as the cathode. Figure 69 is the stability curve at a current density of 100 mA / cm 2 in a 0.5 mol / L H 4 SO 2 solution when used as the oxygen evolution anode material of the tin-doped ruthenium oxide material obtained in Example 27 of the present invention, and Figure 70 is the stability curve at a current density of 200 mA / cm 2 in a 0.5 mol / L H 4 SO 2 solution when used as the oxygen evolution anode material of the tin-doped ruthenium oxide material obtained in Example 27 of the present invention. From Figures 69 and 70, at 100 and 200 mA / cm 2When maintained at a current density for 24 hours and 80 hours respectively, it was found that the current of the tin-doped ruthenium oxide nanomaterial obtained in Example 27 hardly decayed. As shown in Figure 81, the stability of the catalyst material at a high current density is much better than that of commercially available ruthenium dioxide. From this, it was revealed that the tin-doped ruthenium oxide nanomaterial obtained in Example 27 has high stability at a high current density when used as an oxygen evolution reaction anode material. Figure 71 is the stability curve at a current density of 100 mA / cm 2 in a 0.5 mol / L H 4 SO 2 solution when the tin-doped ruthenium oxide material obtained in Comparative Example 7 of the present invention is used as an oxygen evolution anode material, and Figure 72 is the stability curve at a current density of 200 mA / cm 2 in a 0.5 mol / L H 4 SO 2 solution when the tin-doped ruthenium oxide material obtained in Comparative Example 7 of the present invention is used as an oxygen evolution anode material. From Figures 71 and 72, when maintained at current densities of 100 and 200 mA / cm 2 for 24 hours and 100 hours respectively, it was found that at a high current density of 200 mA / cm 2 of the tin-doped ruthenium oxide nanomaterial obtained in Comparative Example 7, an obvious decay in current was observed. As shown in Figure 81, the stability of the catalyst material at a high current density is much better than that of commercially available ruthenium dioxide. From this, it was revealed that the tin-doped ruthenium oxide nanomaterial obtained by adding ammonium citrate has better stability at a high current density than commercially available ruthenium dioxide when used as an oxygen evolution reaction anode material, but not as good as the tin-doped ruthenium oxide nanomaterial obtained in Example 27. Therefore, in this application example, it was observed that when the tin-doped ruthenium oxide nanomaterial formed by adding a multi-ligand polymer is used as an oxygen evolution reaction anode material, both the activity and stability are significantly increased compared to the tin-doped ruthenium oxide nanomaterial formed by adding ammonium citrate as a ligand. Application Example 17 - Test of Activity and Stability

[0162] Using a calomel electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and a three - electrode system with the tin - doped ruthenium oxide nanomaterials obtained in Example 27 and Comparative Example 8 and commercially available ruthenium dioxide as the working electrode, in a 0.5 mol / L H 2 SO 4 solution, the oxygen evolution characteristics of the tin - doped ruthenium oxide nanomaterial of the present invention in water electrolysis were tested, and the obtained polarization curve is shown in Fig. 73. Using a two - electrode system with the tin - doped ruthenium oxide nanomaterials obtained in Example 27 and Comparative Example 8 or commercially available ruthenium dioxide as the anode and a platinum sheet electrode as the cathode, the stability of the oxygen evolution reaction in the water electrolysis of the tin - doped ruthenium oxide nanomaterial of the present invention was tested. From Fig. 73, the tin - doped ruthenium oxide nanomaterials obtained in Example 27 and Comparative Example 8 are excellent in oxygen evolution characteristics (curve B and curve A in Fig. 73) in water electrolysis, far superior to the commercially available ruthenium dioxide material (curve C in Fig. 73), and the overvoltages at a current density of 10 mA / cm 2 were 146 mV and 190 mV respectively, both lower than the 320 mV overvoltage of commercially available ruthenium dioxide. On the other hand, the tin - doped ruthenium oxide nanomaterial obtained in Example 27 is far more excellent in activity when used as the electrode catalyst of the oxygen evolution reaction anode material than the tin - doped ruthenium oxide nanomaterial obtained in Comparative Example 8. Fig. 74 is the stability curve at a current density of 100 mA / cm 2 SO 4 in a solution when the tin - doped ruthenium oxide material obtained in Comparative Example 8 of the present invention is used as the oxygen evolution anode material. From Fig. 74, at 100 mA / cm 2 current density, 2When maintained at a current density for 24 hours, the tin-doped ruthenium oxide nanomaterial obtained in Comparative Example 8 showed a 175 mV attenuation within 24 hours in the stability curve, that is, it was found that the catalytic material had very poor stability at a high current density. From this, it became clear that when the tin-doped ruthenium oxide nanomaterial obtained in Comparative Example 8 was used as an oxygen evolution reaction anode material, its stability at a high current density was much lower than that of the tin-doped ruthenium oxide nanomaterial obtained in Example 27. Therefore, in this application example, it was confirmed that when the tin-doped ruthenium oxide nanomaterial formed by adding a multi-ligand polymer was used as an oxygen evolution reaction anode material, both its activity and stability were significantly improved compared to the tin-doped ruthenium oxide nanomaterial formed without adding a multi-ligand polymer. Application Example 18 - Tests of Activity and Stability

[0163] Using a calomel electrode as the reference electrode, a platinum sheet electrode as the counter electrode, and the transition metal-doped ruthenium oxide nanomaterials obtained in Examples 28 to 38 and commercially available ruthenium dioxide as the working electrode, the oxygen evolution reaction activity of the germanium, indium, antimony, niobium, titanium, zirconium, hafnium, tungsten, molybdenum, tantalum, platinum-doped ruthenium oxide nanomaterials of the present invention in water electrolysis was tested by a three-electrode system. Using a two-electrode system with the transition metal-doped ruthenium oxide nanomaterials obtained in Examples 28 to 38 or commercially available ruthenium dioxide as the anode and a platinum sheet electrode as the cathode, the stability of the oxygen evolution reaction in the water electrolysis of the transition metal-doped ruthenium oxide nanomaterials of the present invention was tested. Figure 75 is a polarization curve obtained by testing the transition metal-doped ruthenium oxide materials obtained in Examples 28 to 32 in a 0.5 mol / L sulfuric acid solution. From Figure 75, the germanium-doped ruthenium oxide nanomaterial produced in Example 28 had a current density of 10 mA / cm in the oxygen evolution reaction. 2The overvoltage at [a certain condition] is 180 mV (curve A in Fig. 75), and the indium-doped ruthenium oxide nanomaterial produced in Example 29 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 200 mV (curve B in Fig. 75), and the antimony-doped ruthenium oxide nanomaterial produced in Example 30 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 180 mV (curve C in Fig. 75), and the niobium-doped ruthenium oxide nanomaterial produced in Example 31 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 180 mV (curve D in Fig. 75), and the titanium-doped ruthenium oxide nanomaterial produced in Example 32 has an overvoltage of 10 mA / cm 2 at [a certain condition] was found to be 250 mV (curve E in Fig. 75). From this, it became clear that the oxygen evolution reaction activity of the transition metal-doped ruthenium oxide nanomaterials produced in Examples 28 to 32 is far superior to that of commercially available ruthenium dioxide (curve F in Fig. 75). Fig. 76 is the polarization curve obtained by testing the transition metal-doped ruthenium oxide materials obtained in Examples 33 to 38 in a 0.5 mol / L H 2 SO 4 solution. The zirconium-doped ruthenium oxide nanomaterial produced in Example 33 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 270 mV (curve A in Fig. 76), and the hafnium-doped ruthenium oxide nanomaterial produced in Example 34 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 270 mV (curve B in Fig. 76), and the tungsten-doped ruthenium oxide nanomaterial produced in Example 35 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 250 mV (curve C in Fig. 76), and the molybdenum-doped ruthenium oxide nanomaterial produced in Example 36 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 240 mV (curve D in Fig. 76), and the tantalum-doped ruthenium oxide nanomaterial produced in Example 37 has an overvoltage of 10 mA / cm 2The overvoltage at [a certain condition] is 220 mV (curve E in Fig. 76), and the platinum-doped ruthenium oxide nanomaterial manufactured in Example 38 has an overvoltage of 10 mA / cm 2 at [a certain condition] of 222 mV (curve F in Fig. 76). From this, it became clear that the oxygen evolution reaction activity of the transition metal-doped ruthenium oxide nanomaterials manufactured in Examples 33 to 38 is far superior to that of commercially available ruthenium dioxide (curve G in Fig. 76). Fig. 77 is the stability curve at a current density of 200 mA / cm² of the transition metal-doped ruthenium oxide materials obtained in Examples 28 to 32. 2 A is the stability curve of germanium-doped ruthenium oxide manufactured in Example 28, B is the stability curve of indium-doped ruthenium oxide manufactured in Example 29, C is the stability curve of antimony-doped ruthenium oxide manufactured in Example 30, D is the stability curve of niobium-doped ruthenium oxide manufactured in Example 31, and E is the stability curve of titanium-doped ruthenium oxide manufactured in Example 32. From Fig. 77, it was found that when maintained at a current density of 200 mA / cm² for 80 hours, the current of the transition metal-doped ruthenium oxide nanomaterials obtained in Examples 28 to 32 hardly decayed. Compared with the commercially available ruthenium dioxide in Fig. 81, in the stability test at a current density of 100 mA / cm², a decay of more than 500 mV was observed after 1 hour of testing. It became clear that the above ruthenium oxide nanomaterials doped with transition metals germanium, indium, antimony, niobium, and titanium have very high stability at high current densities when used as the oxygen evolution reaction anode material. 2 Fig. 78 is the stability curve at a current density of 200 mA / cm² of the transition metal-doped ruthenium oxide materials obtained in Examples 33 to 38. 2 When maintained at a current density of 200 mA / cm² for 80 hours, the current of the transition metal-doped ruthenium oxide nanomaterials obtained in Examples 33 to 38 hardly decayed. Compared with the commercially available ruthenium dioxide in Fig. 81, in the stability test at a current density of 100 mA / cm², a decay of more than 500 mV was observed after 1 hour of testing. It became clear that the above ruthenium oxide nanomaterials doped with transition metals germanium, indium, antimony, niobium, and titanium have very high stability at high current densities when used as the oxygen evolution reaction anode material. Fig. 78 is the stability curve at a current density of 200 mA / cm² of the transition metal-doped ruthenium oxide materials obtained in Examples 33 to 38. 2It is a stability curve at current density. A is the stability curve of zirconium-doped ruthenium oxide manufactured in Example 33, B is the stability curve of hafnium-doped ruthenium oxide manufactured in Example 34, C is the stability curve of tungsten-doped ruthenium oxide manufactured in Example 35, D is the stability curve of molybdenum-doped ruthenium oxide manufactured in Example 36, E is the stability curve of tantalum-doped ruthenium oxide manufactured in Example 37, and F is the stability curve of platinum-doped ruthenium oxide manufactured in Example 38. From Figure 78, 200 mA / cm 2 When held at a current density of 80 hours, it was found that the current of the transition metal-doped ruthenium oxide nanomaterials obtained in Examples 33 to 38 hardly decayed. Compared with the commercially available ruthenium dioxide in Figure 81, 100 mA / cm 2 In the stability test at a current density, a decay of 500 mV or more was observed in the stability curve after a 1-hour test. It was revealed that the ruthenium oxide nanomaterials doped with the above transition metals zirconium, hafnium, tungsten, molybdenum, tantalum, and platinum have very high stability at high current densities when used as oxygen evolution reaction anode materials. Application Example 19 - Tests of Activity and Stability

[0164] Using a calomel electrode as a reference electrode, a platinum sheet electrode as a counter electrode, and the manganese-doped ruthenium oxide nanomaterials obtained in Examples 39 to 43 and commercially available ruthenium dioxide as a working electrode, the oxygen evolution reaction activity of the manganese-doped ruthenium oxide nanomaterials of the present invention in water electrolysis was tested by a three-electrode system. Using a two-electrode system with the manganese-doped ruthenium oxide nanomaterials obtained in Examples 39 to 43 or commercially available ruthenium dioxide as an anode and a platinum sheet electrode as a cathode, the stability of the oxygen evolution reaction of the manganese-doped ruthenium oxide nanomaterials of the present invention in water electrolysis was tested.

[0165] Figure 79 shows the polarization curves obtained by testing the manganese-doped ruthenium oxide materials obtained in Examples 39 to 43 in a 0.5 mol / L sulfuric acid solution. From Figure 79, the manganese-doped ruthenium oxide nanomaterial produced in Example 39 has an overpotential of 310 mV at 10 mA / cm 2 (curve A in Figure 79), and the manganese-doped ruthenium oxide nanomaterial produced in Example 40 has an overpotential of 220 mV at 10 mA / cm 2 (curve B in Figure 79). The manganese-doped ruthenium oxide nanomaterial produced in Example 41 has an overpotential of 220 mV at 10 mA / cm 2 (curve C in Figure 79). The manganese-doped ruthenium oxide nanomaterial produced in Example 42 has an overpotential of 200 mV at 10 mA / cm 2 (curve D in Figure 79). The manganese-doped ruthenium oxide nanomaterial produced in Example 43 has an overpotential of 200 mV at 10 mA / cm 2 (curve E in Figure 79). It was found that the oxygen evolution reaction activities of the manganese-doped ruthenium oxide nanomaterials produced in Examples 39 to 43 are much superior to 320 mV (curve F in Figure 75) of commercially available ruthenium dioxide.

[0166] Figure 80 is the stability curve at a current density of 200 mA / cm of the manganese-doped ruthenium oxide materials obtained in Examples 39 to 43. A is the stability curve of the manganese-doped ruthenium oxide produced in Example 39, B is the stability curve of the manganese-doped ruthenium oxide produced in Example 40, C is the stability curve of the manganese-doped ruthenium oxide produced in Example 41, D is the stability curve of the manganese-doped ruthenium oxide produced in Example 42, and E is the stability curve of the manganese-doped ruthenium oxide produced in Example 43. From Figure 80, at 200 mA / cm 2 ... 2When maintained at a current density for 24 hours, it was found that the current of the manganese-doped ruthenium oxide nanomaterials obtained in Examples 39 to 43 hardly decayed. Compared with the commercially available ruthenium dioxide in Fig. 81, at 100 mA / cm 2 In the stability test at the current density, a decay of more than 500 mV was observed in the stability curve after 1 hour of testing. It was revealed that the above transition metal manganese-doped ruthenium oxide nanomaterials have very high stability at high current densities when used as oxygen evolution reaction anode materials. Regarding the experimental conditions, compared with Application Example 7 and Application Example 8, the optimal reaction conditions for Step 1 and Step 2 are as follows. The heat preservation temperature of the oven is 180 °C, the heat preservation time is 10 h, the heating rate of the muffle furnace is 10 °C / min, the heat preservation temperature is 400 °C, and the heat preservation time is 3 h.

[0167] From Figs. 53 to 81, it was shown that the transition metal-doped ruthenium oxide nanomaterials of the present invention have excellent activity and stability when used as oxygen evolution reaction anode materials in water electrolysis, and are all superior to commercially available ruthenium dioxide materials.

[0168] From the above, when manufacturing transition metal-doped ruthenium oxide nanomaterials by combining a simple hydrothermal treatment method and roasting by adding a polymer having multiple coordination sites, all such materials have rough nanostructures on the surface, and it was fully confirmed that the addition of polymer multi-site ligands significantly improves the electrochemically oxygen evolution reaction activity and stability.

Claims

1. It is a metal-doped ruthenium oxide nanomaterial that is an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial or a transition metal-doped ruthenium oxide nanomaterial, The molecular formula of the acid-insoluble metal-doped ruthenium oxide nanomaterial is M ｘ Ru １－ｘ O ２ and M is an acid-insoluble metal, and the acid-insoluble metal is one or more selected from niobium, titanium, zirconium, hafnium, tungsten, molybdenum, and tantalum, Alternatively, the molecular formula of the transition metal-doped ruthenium oxide nanomaterial is M ｘ Ru １－ｘ O ２ where M is a transition metal, and the transition metal is one selected from Cr, Mn, Ge, In, Sn, Sb, Nb, Ti, Zr, Hf, W, Mo, Ta, and Pt. A metal-doped ruthenium oxide nanomaterial characterized by this.

2. When the metal-doped ruthenium oxide nanomaterial is an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, in the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, the acid-insoluble metal is doped inside the lattice of the ruthenium oxide and replaces a part of the position of ruthenium in the lattice, When the metal-doped ruthenium oxide nanomaterial is a transition metal-doped ruthenium oxide nanomaterial, in the transition metal-doped ruthenium oxide nanomaterial, the transition metal is doped inside the crystal of the ruthenium oxide and replaces a part of the position of ruthenium in the lattice. The metal-doped ruthenium oxide nanomaterial according to Claim 1, characterized by this.

3. In the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, both the acid-insoluble metal and ruthenium are uniformly dispersed, and the surface is rough porous nanoparticles, Or, in the transition metal-doped ruthenium oxide nanomaterial, the transition metal and ruthenium are uniformly dispersed, and the surface is rough nanoparticles, The size of the nanoparticles is 5 to 2000 nm. The metal-doped ruthenium oxide nanomaterial according to Claim 1, characterized by this.

4. In the acid-insoluble metal-doped ruthenium oxide nanomaterial, the doping rate of the acid-insoluble metal is 1 to 50% based on the total molar fraction of the metal in the acid-insoluble metal-doped ruthenium oxide nanomaterial, Or, in the transition metal-doped ruthenium oxide nanomaterial, the doping rate of the transition metal is 1 to 50% based on the total molar fraction of the metal in the transition metal-doped ruthenium oxide nanomaterial. The metal-doped ruthenium oxide nanomaterial according to Claim 1, characterized by this.

5. A method for producing the metal-doped ruthenium oxide nanomaterial according to Claim 1, The metal-doped ruthenium oxide nanomaterial is an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, Step (1) of adding a ligand to a solution containing an acid-insoluble metal source and a ruthenium source to obtain a mixture, mixing the above mixture at a constant temperature in a sealed container for several hours, then opening the lid of the container, evaporating the solvent, scraping the powder to obtain a metal complex precursor; Step (2) of putting the metal complex precursor obtained in step (1) into a muffle furnace, heating it to a desired temperature and then keeping it warm for several hours, naturally cooling and taking it out to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a powder, which is a sol-gel method, characterized by the method.

6. The acid-insoluble metal source is one or more selected from acid-insoluble metal chlorides, acid-insoluble metal organic esterified compounds, acid-insoluble metal carbonyl compounds, acid-insoluble metal oxalates, and acid-insoluble metal ammonium oxalates, The ruthenium source is one or more of ruthenium chloride, acetylacetonatruthenium, ruthenium carbonyl, or ruthenium(III) nitrosyl nitrate, The ligand is a polymer containing a plurality of coordination sites, and the method for producing the metal-doped ruthenium oxide nanomaterial according to claim 5 is characterized in that.

7. The polymer containing a plurality of coordination sites is one or more selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylene diamine, polylactic acid, polypyridine, and polyamide, and the method for producing the metal-doped ruthenium oxide nanomaterial according to claim 6 is characterized in that.

8. In the mixture of step (1), the concentration of the acid-insoluble metal source is 0.01 to 1 mol / L, the concentration of the ruthenium source is 0.1 to 1 mol / L, and the concentration of the complex is 1 to 40 g / L, and the method for producing the metal-doped ruthenium oxide nanomaterial according to claim 5 is characterized in that.

9. In step (2), the heating rate is 1 to 10 °C / min, the desired temperature is 400 to 600 °C, and the heat preservation time is 3 to 6 hours, and the method for producing the metal-doped ruthenium oxide nanomaterial according to claim 5 is characterized in that.

10. The metal-doped ruthenium oxide nanomaterial is an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, Put a solution of an acid-insoluble metal source and a ruthenium source into a hydrothermal treatment kettle, mix until all are dissolved, add an alkali source to obtain a reaction solution, put the hydrothermal treatment kettle into an oven at 100-200 °C, keep warm for 8-16 hours, take out the hydrothermal treatment kettle, naturally cool it to room temperature, then take out the precipitate generated by the reaction, wash it and bake it to obtain a powder, step A; Put the powder baked in step A above into a boat, put the boat into a muffle furnace, set the heating rate to 5-10 °C / min, heat it up to 400-600 °C, keep warm for 2-8 h, then naturally cool it to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a black powder sample, step B, which includes; In step A, in the reaction solution, the concentration of the acid-insoluble metal source is 0.001-1 mol / L, the concentration of the ruthenium source is 0.1-1 mol / L, and the concentration of the alkali source is 1-5 g / L. It is a solvothermal method, and the method for manufacturing a metal-doped ruthenium oxide nanomaterial according to claim 1 is characterized by this.

11. The metal-doped ruthenium oxide nanomaterial is an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, and the manufacturing method is as follows: Put ruthenium oxide and an oxide of an acid-insoluble metal into a ball milling tank, perform ball milling 2-3 times for 3-6 hours each time to obtain a precursor powder, put the precursor powder into a boat, put the boat into a muffle furnace, set the heating rate to 5-10 °C / min, heat it up to 400-800 °C, keep warm for 6-12 h, then naturally cool it to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a black powder sample, including the step; The molar ratio of the ruthenium oxide to the oxide of the acid-insoluble metal is 99:1-1:

1. It is a ball milling method, and the method for manufacturing a metal-doped ruthenium oxide nanomaterial according to claim 1 is characterized by this.

12. Use of the metal-doped ruthenium oxide nanomaterial according to any one of claims 1-4 as an electrode material.

13. The use is characterized in that it is used as an oxygen evolution anode material in the water electrolysis of the metal-doped ruthenium oxide nanomaterial, and the use according to claim 12 is characterized by this.

14. The metal-doped ruthenium oxide nanomaterial is a transition metal-doped ruthenium oxide nanomaterial. After adding a soluble transition metal source to a solution containing a soluble ruthenium source and mixing them, a polymer containing a plurality of ligand sites is added and further mixed to obtain a mixture. The mixture is transferred to a hydrothermal treatment autoclave, kept warm in a constant temperature oven for several hours, taken out, naturally cooled to room temperature, washed, centrifuged, and then dried to obtain a precursor containing a transition metal (Step (1)). A hydrothermal treatment method comprising: Step (2) of putting the precursor containing a transition metal obtained in Step (1) into a muffle furnace, raising the temperature to a desired temperature, keeping warm for several hours, naturally cooling, and then taking out to obtain the transition metal-doped ruthenium oxide nanomaterial as a powder. The method for producing a metal-doped ruthenium oxide nanomaterial according to claim 1, characterized in that.

15. The soluble transition metal source is one or more selected from transition metal chlorides, expensive compounds of transition metals, organic esterified products of transition metals, carbonyl compounds of transition metals, and oxalates of transition metals. The ruthenium source is one or more selected from ruthenium chloride, acetylacetonato ruthenium, ruthenium carbonyl, or ruthenium(III) nitrosyl nitrate. The polymer containing a plurality of ligand sites is one or more selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylene diamine, polylactic acid, polypyridine, and polyamide. The method for producing a metal-doped ruthenium oxide nanomaterial according to claim 14, characterized in that.

16. In the mixture of Step (1), the concentration of the transition metal source is 0.001 to 1 mol / L, the concentration of the ruthenium source is 0.1 to 1 mol / L, and the concentration of the polymer is 1 to 50 g / L. The method for producing a metal-doped ruthenium oxide nanomaterial according to claim 15, characterized in that.

17. In Step (1), the constant temperature is 100 to 180 °C and the heat preservation time is 4 to 10 h. In Step (2), the heating rate is 1 to 10 °C / min, the desired temperature is 300 to 500 °C, and the heat preservation time is 3 to 5 h. The method for producing a metal-doped ruthenium oxide nanomaterial according to claim 15, characterized in that.

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