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.

Claims

[Claim 1] Metal-doped ruthenium oxide nanomaterial, These are acid-insoluble metal oxide-doped ruthenium oxide nanomaterials or transition metal-doped ruthenium oxide nanomaterials. The molecular formula of the aforementioned acid-insoluble metal oxide-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, or The molecular formula of the transition metal-doped ruthenium oxide nanomaterial is M ｘ Ru １－ｘ O ２ And, M is a transition metal, and the transition metal is selected from Cr, Mn, Ge, In, Sn, Sb, Nb, Ti, Zr, Hf, W, Mo, Ta, and Pt. 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 mole fraction of the metal in the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, or The metal-doped ruthenium oxide nanomaterial is characterized in that, in the transition metal-doped ruthenium oxide nanomaterial, the doping rate of the transition metal is 1 to 50% based on the total mole fraction of the metal in the transition metal-doped ruthenium oxide nanomaterial. [Claim 2] When the metal-doped ruthenium oxide nanomaterial is an acid-insoluble metal oxide-doped ruthenium oxide nanomaterial, the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial is doped into the lattice of ruthenium oxide, thereby substituting for some of the positions of ruthenium in the lattice. The metal-doped ruthenium oxide nanomaterial according to claim 1, wherein, in the transition metal-doped ruthenium oxide nanomaterial, the transition metal is doped into the interior of the ruthenium oxide crystal to replace a portion of the positions of ruthenium in the lattice. [Claim 3] A method for producing a metal-doped ruthenium oxide nanomaterial according to claim 1, The aforementioned metal-doped ruthenium oxide nanomaterial is an acid-poorly soluble metal oxide-doped ruthenium oxide nanomaterial, and the manufacturing method is Step (1) involves adding a ligand to a solution containing an acid-insoluble metal source and a ruthenium source to obtain a mixture, mixing the mixture in a sealed container at a constant temperature for several hours, then opening the lid of the container, evaporating the solvent, scraping off the powder, and obtaining a metal complex precursor. A manufacturing method characterized by being a sol-gel method, comprising step (2) placing the metal complex precursor obtained in step (1) into a muffle furnace, raising the temperature to 400-600°C, maintaining the temperature for 3-6 hours, allowing it to cool naturally, and then removing it to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a powder. [Claim 4] The acid-insoluble metal source is one or more selected from acid-insoluble metal chlorides, acid-insoluble metal organic esters, acid-insoluble metal carbonyl compounds, acid-insoluble metal oxalates, and acid-insoluble metal ammonium salts. The ruthenium source is one or more of the following: ruthenium chloride, acetylacetonatorthenium, ruthenium carbonyl, or ruthenium(III) nitrate nitrosyl. The method for producing a metal-doped ruthenium oxide nanomaterial according to claim 3, characterized in that the ligand is a polymer containing multiple coordination sites. [Claim 5] The method for producing metal-doped ruthenium oxide nanomaterials according to claim 4, characterized in that the polymer containing the plurality of coordination sites is one or more selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylenediamine, polylactic acid, polypyridine, and polyamide. [Claim 6] The method for producing metal-doped ruthenium oxide nanomaterials according to claim 3, characterized in that, 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 ligand is 1 to 40 g / L. [Claim 7] The method for producing metal-doped ruthenium oxide nanomaterials according to claim 3, characterized in that, in step (2), the rate of heating is 1 to 10°C / min. [Claim 8] A method for producing a metal-doped ruthenium oxide nanomaterial according to claim 1, The aforementioned metal-doped ruthenium oxide nanomaterial is an acid-poorly soluble metal oxide-doped ruthenium oxide nanomaterial, and the manufacturing method is Step A involves placing solutions of an acid-insoluble metal source and a ruthenium source into a hydrothermal treatment vessel, mixing until everything is dissolved, adding an alkali source to obtain a reaction solution, placing the hydrothermal treatment vessel in an oven at 100-200°C, maintaining the temperature for 8-16 hours, removing the hydrothermal treatment vessel, allowing it to cool naturally to room temperature, then removing the precipitate formed by the reaction, washing and baking it to obtain a powder. Step B is a solvothermal method comprising: placing the powder baked in step A into a boat; placing the boat into a muffle furnace; setting the heating rate to 5-10°C / min; raising the temperature to 400-600°C; maintaining the temperature for 2-8 hours; and then allowing it to cool naturally to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a black powder sample. A manufacturing method characterized in that, in step A, the concentration of the acid-insoluble metal source in the reaction solution 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 alkali source is 1 to 5 g / L. [Claim 9] A method for producing a metal-doped ruthenium oxide nanomaterial according to claim 1, The aforementioned metal-doped ruthenium oxide nanomaterial is an acid-poorly soluble metal oxide-doped ruthenium oxide nanomaterial, and the manufacturing method is as follows: The ball milling method includes the steps of: placing ruthenium oxide and an acid-insoluble metal oxide in a ball milling tank; performing ball milling for 3 to 6 hours 2 to 3 times to obtain a precursor powder; placing the precursor powder in a boat; placing the boat in a muffle furnace; setting the heating rate to 5 to 10°C / min; raising the temperature to 400 to 800°C; maintaining the temperature for 6 to 12 hours; and then allowing it to cool naturally to obtain the acid-insoluble metal oxide-doped ruthenium oxide nanomaterial as a black powder sample. A method for producing metal-doped ruthenium oxide nanomaterials, characterized in that the molar ratio of ruthenium oxide to an acid-insoluble metal oxide is 99:1 to 1:

1. [Claim 10] Use of the metal-doped ruthenium oxide nanomaterial according to claim 1 or 2 as an electrode material. [Claim 11] The use according to claim 10, characterized in that the metal-doped ruthenium oxide nanomaterial is used as an oxygen-evolving anode material in water electrolysis. [Claim 12] A method for producing a metal-doped ruthenium oxide nanomaterial according to claim 1, The metal-doped ruthenium oxide nanomaterial is a transition metal-doped ruthenium oxide nanomaterial, and the manufacturing method is Step (1) involves adding a water-soluble transition metal source to a solution containing a water-soluble ruthenium source and mixing it, then adding a polymer containing multiple coordination sites and mixing further to obtain a mixture, transferring the mixture to a hydrothermal treatment vessel, keeping it warm in a constant temperature oven for several hours, removing it, allowing it to cool naturally to room temperature, washing it, centrifuging it, and then drying it to obtain a precursor containing a transition metal. A manufacturing method characterized by a hydrothermal treatment method comprising step (2), which involves placing the transition metal-containing precursor obtained in step (1) into a muffle furnace, raising the temperature to 300 to 500°C, maintaining the temperature for 3 to 5 hours, allowing it to cool naturally, and then removing it to obtain the transition metal-doped ruthenium oxide nanomaterial as a powder. [Claim 13] The aforementioned water-soluble transition metal source is one or more selected from transition metal chlorides and transition metal oxalates. The water-soluble ruthenium source is one or more selected from ruthenium chloride, acetylacetonatorthenium, ruthenium carbonyl, or ruthenium(III) nitrate nitrosyl. The method for producing a metal-doped ruthenium oxide nanomaterial according to claim 12, characterized in that the polymer containing the plurality of coordination sites is one or more selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylenediamine, polylactic acid, polypyridine, and polyamide. [Claim 14] The method for producing metal-doped ruthenium oxide nanomaterials according to claim 13, characterized in that, in the mixture of step (1), the concentration of the water-soluble transition metal source is 0.001 to 1 mol / L, the concentration of the water-soluble ruthenium source is 0.1 to 1 mol / L, and the concentration of the polymer is 1 to 50 g / L. [Claim 15] In step (1), the temperature inside the constant temperature oven is 100 to 180°C, and the holding time is 4 to 10 hours. The method for producing metal-doped ruthenium oxide nanomaterials according to claim 13, characterized in that in step (2), the rate of heating is 1 to 10°C / min.

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