CN113265681A - Atom-level uniformly-dispersed ruthenium-based multi-element metal oxide material and preparation method and application thereof - Google Patents

Atom-level uniformly-dispersed ruthenium-based multi-element metal oxide material and preparation method and application thereof Download PDF

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CN113265681A
CN113265681A CN202110379704.4A CN202110379704A CN113265681A CN 113265681 A CN113265681 A CN 113265681A CN 202110379704 A CN202110379704 A CN 202110379704A CN 113265681 A CN113265681 A CN 113265681A
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张波
温蕴周
黄睿
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Fudan University
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Abstract

The invention belongs to the technical field of electrocatalysts, and particularly relates to an atom-level uniformly-dispersed ruthenium-based multi-element metal oxide nano catalyst, and a preparation method and application thereof. The ruthenium-based multi-element metal oxide material is prepared by a sol-gel method, Ru is used as a base metal, and a second metal A and a third metal M are introduced; wherein the metal A is one of alkali metals such as Na and K and alkaline earth metals, the metal M is one or two of transition metals such as Ir, W and Pd or main group metals of Pb, Sn, Sb and Si; the invention overcomes the phase separation problem in the preparation of the multi-metal composite catalyst and realizes the atomic-level uniform dispersion of the multi-metal. The metals A and M in the composite oxide catalyst with the atomic-scale uniform dispersion are beneficial to regulating and controlling the electronic structure and the local structure of Ru, so that the oxygen evolution activity and the stability of the catalyst are improved. The method has simple process, can realize the oxygen evolution catalyst with high activity and high stability, and has wide application prospect.

Description

Atom-level uniformly-dispersed ruthenium-based multi-element metal oxide material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to an atom-level uniformly-dispersed ruthenium-based multi-element metal oxide nano catalyst, and a preparation method and application thereof.
Background
The Oxygen Evolution Reaction (OER) is an anodic reaction in devices for hydrogen production by water electrolysis, carbon dioxide electroreduction, electrowinning, and the like. Since the reaction involves a complex multistep electron transfer process, even with the presently optimal IrO2The catalyst still has higher overpotential and the reaction rate is slower. On the other hand, the proton exchange membrane water electrolysis device is a novel water electrolysis device and has the advantages of high current density, quick system response, low gas permeability and the like. However, the proton exchange membrane used by the method has strong acidity, so that the OER catalyst loaded on the proton exchange membrane is corroded in the reaction process, and the electrolytic stability is influenced.
Studies have shown that Ru-based oxides exhibit higher OER activity but are less stable. This is mainly because the reaction of Ru-based oxides produces high-valent Ru+n（n >4) A species which has a high OER activity but which is easily dissolved, thereby causing deterioration in stability of the Ru-based oxide. In addition, frequent adsorption/desorption processes on the Ru sites for the OER intermediate also cause changes in the Ru valence state, thereby reducing the stability of the Ru-based oxide catalyst. The second metal and the third metal are introduced to construct the Ru-based composite metal oxide, and the electronic structure and the local structure of Ru can be regulated and controlled, so that the adsorption and desorption processes of an OER intermediate product on Ru sites can be regulated and controlled, and the high activity and the stability of the Ru-based oxide catalyst can be realized at the same time.
Disclosure of Invention
The invention aims to provide an atom-level uniformly-dispersed ruthenium-based multi-element metal oxide material with high catalytic activity and high stability, and a preparation method and application thereof.
The ruthenium-based multi-element metal oxide material provided by the invention is prepared by a sol-gel method, Ru is taken as a basic metal material,introducing a second metal A and a third metal M; is denoted as ARuMOx(ii) a Wherein, the atom percentage of Ru is 20-80%, the second element metal A is one of alkali metal and alkaline earth metal such as Na, K, Mg, Ca, Sr, Ba, etc., the atom percentage is 0-50% (preferably 1-50%), the third element metal M is one or two of transition metal such as Ir, W, Pd, Mo, Ag, Mn, etc., or main group metal such as Pb, Sn, Sb, Si, etc., the atom percentage is 15-70%.
The ruthenium-based multi-element metal oxide material provided by the invention is prepared by adopting a sol-gel method, and comprises the following specific steps:
(1) preparing a mixed solution of ruthenium-based metal salts: weighing 1-5 g of ruthenium salt, 0-2.5 g of alkaline earth metal salt and 1-5 g of transition metal salt or main group metal salt, dissolving in 50-200 mL of organic solvent, and placing the mixed solution in a refrigerator at-10-4 ℃ for 0-5 hours;
(2) adding an epoxy compound: slowly dripping 10-100 mL of epoxy compound and 1-20 mL of deionized water into the mixed solution at the speed of 0.5-50 mL/min, and stirring to fully mix;
(3) standing and precipitating: standing the mixed solution for 1-7 days to form jelly-like gel/precipitate in the solution, adding acetone, centrifuging to obtain precipitate, and washing the precipitate with acetone for 3-6 times; and drying;
(4) high-temperature calcination: the dried product is put into a tubular furnace, the temperature is raised to 400-800 ℃ at the temperature rise rate of 5-20 ℃/min in the air atmosphere, and the calcination is carried out for 0.5-6 hours to prepare the ruthenium-based multi-element metal oxide material ARuMOx。
In the invention, the ruthenium salt is one of hydrated ruthenium trichloride, trihydrate ruthenium trichloride, anhydrous ruthenium trichloride, acetylacetone ruthenium and nitrosyl ruthenium nitrate.
In the present invention, the alkaline earth metal salt is 1-3 of hydrochloride, nitrate, sulfate or acetate of Na, K, Mg, Ca, Sr and Ba, such as NaCl, KNO3、MgCl2·6H2O、MgCl2、Ca(CH3COO)2·H2O、SrCl2·6H2O, and the like.
In the present invention, the transition metal or main group metal salt is 1 to 3 kinds of hydrochloride, nitrate, sulfate, acetate, perchlorate or chlorate of metal such as Ir, W, Pd, Mo, Cu, Al, Ag, Mn, Pb, Sn, Sb, Si, such as Na3IrCl6·xH2O、MoCl5、CuCl2、Al(NO3)3、AlCl3、MnCl2、Pb(CH3COO)2·3H2O、SiCl4、SnCl4、SnCl4·5H2O, and the like.
In the invention, the organic solvent is one of methanol, ethanol, N-propanol, isopropanol, glycol, glycerol, acetone, N-dimethylformamide, N-dimethylhexanamide, dimethyl sulfoxide and tetrahydrofuran.
In the invention, the epoxy compound is one of 1, 2-epoxypropane, 1, 2-epoxybutane, epichlorohydrin and epoxy bromopropane.
The ruthenium-based multi-element metal oxide material prepared by the invention overcomes the phase separation problem in the preparation of the multi-metal composite catalyst and realizes the atomic-level uniform dispersion of multi-element metal. The metals A and M in the composite oxide catalyst with the atomic-scale uniform dispersion are beneficial to regulating and controlling the electronic structure and the local structure of Ru, so that the oxygen evolution activity and the stability of the catalyst are improved. The method has simple process, can realize the oxygen evolution catalyst with high activity and high stability, and has wide application prospect.
The ruthenium-based multi-element metal oxide material prepared by the invention can be used as an oxygen evolution reaction catalyst electrode material, and the specific preparation steps of the oxygen evolution reaction catalyst electrode are as follows: dispersing a ruthenium-based multi-element metal oxide material and a conductive agent in a mixed solvent of an organic solvent and water, adding a binder, and coating catalyst slurry on a catalyst carrier after ultrasonic dispersion; after being dried, the anode can be used as an anode for electrochemical oxygen evolution reaction. Wherein the conductive agent is carbon black, carbon nano tube, graphene and the like, and the specific weight of the conductive agent is 10-30%. The adhesive is 5% perfluorosulfonic acid polymer solution, and the specific gravity of the adhesive in the catalyst slurry is 5-30%. The catalyst carrier is carbon paper, carbon cloth, carbon felt, goldBelongs to foam, metal foil and the like, and the loading amount of the catalyst is 2-50 mg/cm2. The organic solvent is methanol, ethanol, isopropanol, acetone, tetrahydrofuran, etc.
The ruthenium-based multi-element metal oxide material prepared by the invention can be used as an anode catalyst material in a water electrolysis device based on a proton exchange membrane. Specifically, the water electrolysis device based on the proton exchange membrane takes the ruthenium-based multi-element metal oxide material as an anode catalyst, takes a platinum carbon catalyst with 20-100% of platinum content as a cathode catalyst, and adopts a perfluorinated sulfonic acid resin proton exchange membrane (Nafion) with the thickness of 25-250 mu m®、Aquivion®Or proton exchange membrane of other brands) as a diaphragm, carbon paper with a microporous layer and a porous sintered titanium plate are respectively used as a cathode gas diffusion layer and an anode gas diffusion layer, a titanium plate or a graphite plate with a carved flow field is used as a cathode end plate and an anode end plate, pure water or 0.05-2 mol/L sulfuric acid is introduced as electrolyte, and the obtained proton exchange membrane water electrolysis device is assembled.
The preparation method of the membrane electrode assembly in the water electrolysis device based on the proton exchange membrane comprises the following specific steps:
dispersing ruthenium-based multi-element metal oxide material in an organic solvent, adding a binder, performing ultrasonic dispersion, and spraying the catalyst slurry on a polytetrafluoroethylene film with the thickness of 10-150 mu m or directly on a proton exchange membrane. Wherein, the weight ratio of the binder is 10-40%, and the loading capacity of the catalyst is 0.3-3 mg/cm2. After drying, covering the catalyst-loaded polytetrafluoroethylene film on a proton exchange membrane, carrying out hot pressing at the temperature of 110-.
And dispersing a platinum-carbon catalyst with the platinum content of 20-100% in an organic solvent, adding a binder, performing ultrasonic dispersion, and spraying the catalyst slurry on conductive carbon paper with the thickness of 80-250 mu m or directly spraying the catalyst slurry on a proton exchange membrane. Wherein, the weight ratio of the binder is 10-40%, and the platinum loading capacity of the catalyst is 0.1-1.5 mg/cm2. After drying, coating the carbon paper with the supported catalyst on the proton exchange membrane with the supported catalystAnd hot-pressing at 110-260 deg.C under 2-20 MPa for 1-20 min to obtain the membrane electrode assembly of the device.
The ruthenium-based multi-element metal oxide material prepared by the method can also be used as an electrode material of an electrochemical carbon dioxide reduction reaction catalyst in an electrochemical carbon dioxide epoxy device. Specifically, the carbon dioxide epoxy device takes a ruthenium-based multi-component metal oxide material as an anode catalyst and takes a copper, silver, gold or ruthenium-based multi-component metal oxide material as a cathode catalyst. Using an anion exchange membrane (Fumasep) with a thickness of 25-250 μm®、Sustanion®Or anion exchange membranes of other brands) as a diaphragm, carbon paper with a microporous layer and a porous sintered titanium plate are respectively used as a cathode gas diffusion layer and an anode gas diffusion layer, a titanium plate or a graphite plate with a carved flow field is used as a cathode end plate and an anode end plate, and pure water or 0.05-10 mol/L potassium hydroxide solution is introduced as electrolyte to assemble the electrochemical carbon dioxide epoxy device.
The preparation method of the membrane electrode assembly in the electrochemical carbon dioxide epoxy device comprises the following specific steps:
dispersing ruthenium-based multi-element metal oxide material and a conductive agent in a mixed solvent of an organic solvent and water, adding a binder, performing ultrasonic dispersion, and coating or spraying catalyst slurry on a catalyst carrier. After drying, the carbon dioxide can be used as a cathode of electrochemical carbon dioxide reduction reaction. Wherein the conductive agent is carbon black, carbon nano tube, graphene and the like, and the specific weight of the conductive agent is 10-30%. The adhesive is 5% perfluorosulfonic acid polymer solution, and the specific gravity of the adhesive in the catalyst slurry is 5-30%. The catalyst carrier is carbon paper, carbon cloth, carbon felt, metal foam, metal foil and the like, and the loading capacity of the catalyst is 2-50 mg/cm2。
Drawings
FIG. 1 shows SrRuIrOxTransmission electron microscope photograph of ternary metal oxide material.
FIG. 2 shows SrRuIrOxElemental spectrum distribution of ternary metal oxide materials.
FIG. 3 shows SrRuIrOxAn X-ray diffraction pattern of a ternary metal oxide material.
FIG. 4 is a graph for SrRuIrOxAnd (3) performing wavelet transformation on the expanded X-ray absorption fine structure spectrum of the ternary metal oxide material.
FIG. 5 shows SrRuIrOxLinear sweep voltammetry of ternary metal oxide materials and its interaction with commercial RuO2、IrO2And comparing the activity of the materials.
FIG. 6 shows SrRuIrOxThe OER stability curve of the ternary metal oxide material and the structural schematic diagram of the catalyst used for the proton exchange membrane water electrolysis device.
FIG. 7 shows RuIrOxAnd SrRuOxAn X-ray diffraction pattern of a binary metal oxide material.
FIG. 8 shows RuIrOxAnd SrRuOxLinear sweep voltammograms of binary metal oxide materials and their use with commercial RuO2、IrO2And comparing the activity of the materials.
FIG. 9 shows RuWOxThermogravimetric analysis of binary metal oxide material before annealing.
FIG. 10 shows RuWOxTransmission electron microscope photographs of binary metal oxide materials. A scale: 5 nm.
FIG. 11 shows RuWOxAn X-ray diffraction pattern of a binary metal oxide material.
FIG. 12 shows RuWOxAnd (3) performing Fourier transform on the expanded X-ray absorption fine structure spectrum of the binary metal oxide material.
FIG. 13 shows RuWOxLinear sweep voltammograms of binary metal oxide materials and their use with commercial RuO2、IrO2And comparing the activity of the materials.
Fig. 14 is a structural view of a proton exchange membrane water electrolysis apparatus.
FIG. 15 shows SrRuIrOxThe electrochemical performance diagram and the stability curve of the proton exchange membrane water electrolysis device assembled by taking the ternary metal oxide material as the anode catalyst and the 40% Pt/C catalyst as the cathode catalyst.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
(1) A ruthenium-based ternary metal oxide material based on a sol-gel method is prepared by the following steps: 1 g of ruthenium trichloride (RuCl) was weighed3) 0.5 g of sodium chloroiridate (Na)3IrCl6) And 0.8g of strontium chloride (SrCl)2) And dissolved in 30 mL of N, N-dimethylformamide solvent, and the mixed solution was left in a refrigerator at 4 ℃ for 2 hours. Then, 5mL of propylene oxide and 2mL of deionized water were added dropwise to the solution at rates of 2.5 mL/min and 1mL/min, respectively, and sufficiently mixed by stirring. After the solution is kept stand for 1 day, acetone is added to quench the reaction, and after the solution is kept stand in the acetone for 1 day, the solution is centrifuged to obtain a precipitate product, and the precipitate product is washed by the acetone. After the product is dried, putting the product into a tube furnace, heating to 500 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and calcining for 1 hour to prepare SrRuIrOxA ternary metal oxide material. As shown in fig. 1 and 2, SrRuIrOxThe composite oxide is in the shape of nano-particles, the size range is 3-5 nm, and ruthenium, iridium, strontium and oxygen elements in the oxide are in homogeneous distribution. As shown in fig. 3, SrRuIrOxAll the characteristic peaks of X-ray diffraction of the composite oxide material can be assigned to RuO2(PDF # 43-1027). Further using the extended X-ray absorption fine structure spectrum to SrRuIrOxCharacterization (figure 4) was carried out to find that the atoms in the catalyst exhibited a homogeneous distribution at the atomic level.
（2）SrRuIrOxPreparing a ternary metal oxide catalyst electrode: 50 mg of SrRuIrOxThe ternary metal oxide material and 20 mg of carbon black are dispersed in 10 mL of a mixed solvent of ethanol and water (volume ratio of 1: 5), 0.2mL of a 5wt% perfluorosulfonic acid resin monomer solution is added, and after 3 hours of ultrasonic treatment, the catalyst slurry is dropwise coated on a glassy carbon electrode with the diameter of 3 cm. After natural drying, preparing the oxygen evolution reaction catalyst electrode, wherein the loading capacity of the catalyst is 2.5 mg/cm2. As shown in fig. 5, the catalyst electrode was at 0.5M H2SO410 mA/cm in the aqueous solution2The potential of the oxygen evolution reaction current is 1.42V, namely the overpotential is 190 mV, which is obviously superior to that of the commercial RuO2And IrO2A catalyst. As shown in FIG. 6, at a constant current of 1500 hoursDuring the test, the potential does not increase obviously, which indicates that the catalyst electrode has excellent stability.
Example 2
(1) A ruthenium-based binary metal oxide material based on a sol-gel method is prepared by the following steps: 2 g of ruthenium trichloride hydrate (RuCl) were weighed out3·xH2O) and 1 g of sodium chloroiridate hydrate (Na)3IrCl6·xH2O), or 2 g of ruthenium trichloride hydrate (RuCl)3·xH2O) and 1.6 g of strontium chloride hexahydrate (SrCl)2·6H2O), was dissolved in 100 mL of N, N-dimethylformamide solvent, and the mixed solution was left in a refrigerator at-4 ℃ for 2 hours. Then, 20 mL of propylene oxide and 4 mL of deionized water were simultaneously dropped into the solution at respective dropping rates of 5mL/min and 1mL/min, and sufficiently mixed by stirring. After the solution is kept stand for 12 h, acetone is added to quench the reaction, and the solution is soaked in acetone for 3 days, and then the precipitated product is centrifugally cleaned by acetone. After the product is dried, putting the product into a tube furnace, heating to 525 ℃ at the heating rate of 5 ℃/min in the air atmosphere, calcining for 1 hour, and preparing to obtain RuIrOxAnd SrRuOxA binary metal oxide material. As shown in fig. 7, RuIrOxAnd SrRuOxAll the main X-ray diffraction characteristic peaks of the binary oxide material can be attributed to RuO2(PDF # 43-1027). In addition, a small amount of strontium ruthenate (PDF # 43-0472), strontium carbonate (PDF # 05-0418) and metallic ruthenium (PDF # 06-0663) impurities are generated in the synthesis process.
(2) Preparing a hydrated metal doped ruthenium-iridium composite oxide catalyst electrode: 50 mg of RuIrOxOr SrRuOxThe binary metal oxide material and 15 mg of carbon black are dispersed in 5mL of a mixed solvent of ethanol and water (volume ratio of 1: 4), 100 μ L of a 5wt% perfluorosulfonic acid resin monomer solution is added, and after 30 minutes of ultrasonic treatment, the catalyst slurry is drop-coated on carbon paper. After natural drying, preparing the oxygen evolution reaction catalyst electrode, wherein the loading capacity of the catalyst is 5 mg/cm2. As shown in fig. 8, the catalyst electrode was at 0.5M H2SO410 mA/cm in the aqueous solution2Potential of oxygen evolution reaction current1.46V, namely 230 mV of overpotential, is remarkably superior to that of commercial RuO2And IrO2A catalyst.
Example 3
(1) A ruthenium-based binary metal oxide material based on a sol-gel method is prepared by the following steps: 1.04 g of ruthenium trichloride hydrate (RuCl) was weighed3·xH2O), 0.58 g of tungsten hexachloride (WCl)6) And 5.8 g of tetra-n-butylammonium bromide (C)16H36BrN) was dissolved in 30 mL of anhydrous ethanol, and the mixed solution was left in a 0 ℃ refrigerator for 2 hours. Then, 5mL of propylene oxide and 2mL of deionized water were added dropwise to the solution at rates of 5mL/min and 2mL/min, respectively, and sufficiently mixed by stirring. After the solution is kept stand for 1 day, acetone is added to quench the reaction, and after the solution is kept stand in the acetone for 3 days, the solution is centrifuged to obtain a precipitate product, and the precipitate product is washed by the acetone. After the product is dried, the product is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and the product is calcined for 1 hour (figure 9), thus obtaining RuWOxA binary metal oxide material. As shown in fig. 10, RuWOxThe binary oxide material is nanoparticles with a particle size of about 5 nm. As can be seen from FIG. 11, the main X-ray diffraction characteristic peaks of the catalyst can be assigned to RuO2(PDF # 43-1027). By adjusting the ratio of Ru to W precursor, a little phase separation phenomenon can occur in the catalyst synthesis process, and the mass ratio of Ru to W is optimal at 5: 1. Further using extended X-ray absorption fine structure spectrum to the RuWOxCharacterization of the binary metal oxide catalyst shows that the W atom is in rutile RuO2The structure shows uniform distribution at the atomic level, and the original rutile structure has increased disorder degree (figure 12).
（2）RuWOxPreparing a binary metal oxide catalyst electrode: 50 mg of RuWOxThe binary metal oxide material and 20 mg of carbon black are dispersed in 10 mL of mixed solvent of isopropanol and water (volume ratio is 1: 5), 0.2mL of 5wt% perfluorosulfonic acid resin monomer solution is added, and after 2 hours of ultrasonic treatment, the catalyst slurry is dropwise coated on a glassy carbon electrode with the diameter of 3 cm. After natural drying, preparing the oxygen evolution reaction catalyst electrode and the negative electrode of the catalystThe loading capacity is 2.5 mg/cm2. As shown in fig. 13, the catalyst electrode was at 0.5M H2SO410 mA/cm in the aqueous solution2The potential of the oxygen evolution reaction current is 1.44V, namely the overpotential is 210 mV, which is obviously superior to that of the commercial RuO2And IrO2The catalyst does not use noble metal iridium, so that the synthesis cost is greatly reduced.
Example 4
(1) The preparation of anode catalyst supported membrane electrode of proton exchange membrane water electrolysis device: weighing SrRuIrOx0.8g of ternary metal oxide catalyst is dispersed in 100 mL of isopropanol, 2mL of 5wt% perfluorosulfonic acid resin monomer solution is added, and the mixture is fully dispersed by ultrasonic. The catalyst slurry was sprayed using a spray gun to a thickness of 50 μm and an area of 200 cm2Drying the polytetrafluoroethylene film, weighing, and repeating the above operations until the loading amount of the catalyst is 2 mg/cm2. Then coating a polytetrafluoroethylene film with the loaded catalyst on the surface of 200 cm2Nafion (R) of®And hot pressing the 115 type proton exchange membrane for 3 min at 130 ℃ and under the pressure of 5 Mpa, and removing the polytetrafluoroethylene film after pressure maintaining and cooling to obtain the catalyst-loaded proton exchange membrane anode.
(2) Preparing a cathode gas diffusion electrode of a proton exchange membrane water electrolysis device: weighing 0.4 g of platinum-carbon catalyst with platinum content of 40 percent, dispersing in ethanol, adding 2.5mL of 5wt percent perfluorosulfonic acid resin monomer solution, fully performing ultrasonic dispersion, spraying catalyst slurry on conductive carbon paper with the thickness of 150 mu m, drying, weighing, and repeating the operation until the platinum loading capacity of the catalyst is 0.1 mg/cm2. And drying to obtain the cathode gas diffusion electrode.
(3) Assembling a proton exchange membrane water electrolysis device: covering a gas diffusion electrode (2) which is loaded with a catalyst on the loaded SrRuIrOxHot pressing the proton exchange membrane (1) of the catalyst for 3 min at 130 ℃ and under the pressure of 2 Mpa to obtain the membrane electrode assembly for the proton exchange membrane electrolyzer. Then, the titanium end plate (S-shaped flow channel, flow field area 25 cm)2) Porous sintered titanium plate (area 25 cm)2) Sealing the containerThe rings and the like are sequentially assembled on both sides of the membrane electrode assembly (the structure thereof is shown in fig. 14). And (3) fastening the end plates at the two sides by using eight M6 hexagon socket head cap screws and matched hexagon nuts, wherein the fastening torsion is 0.8N/M, and then finishing the assembly of the proton exchange membrane water electrolysis device. Deionized water with the temperature of 80 ℃ is introduced into one side of the anode, and voltage is applied to two sides of the titanium flow field end plate, so that hydrogen and oxygen can be prepared by water electrolysis. The electrochemical performance is shown in fig. 15. The device reaches 1A cm-2The voltage required for the electrolysis current was only 1.50V and there was no significant degradation in performance over a continuous electrolysis period of several hundred hours.
Example 5
A ruthenium-based quaternary metal oxide material based on a sol-gel method is prepared by the following steps: 1.5 g of ruthenium trichloride (RuCl) are weighed out3) 1 g of lead acetate trihydrate (Pb (CH)3COO)2·3H2O), 0.8g of tin tetrachloride pentahydrate (SnCl)4·5H2O) and 0.8g of magnesium chloride (MgCl)2) And dissolved in 50 mL of ethanol solvent. Then, 5mL of butylene oxide and 2mL of deionized water were added dropwise to the solution at rates of 5mL/min and 2mL/min, respectively, and sufficiently mixed by stirring. After the solution is kept stand for 1 day, acetone is added to quench the reaction, and after the solution is kept stand in the acetone for 1 day, the solution is centrifuged to obtain a precipitate product, and the precipitate product is washed by the acetone. After the product is dried, putting the product into a tube furnace, heating to 800 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and calcining for 2 hours to prepare MgRuPbSnOxA quaternary metal oxide material.
Example 6
(1) Preparation of an anode catalyst loaded membrane electrode of an anion exchange membrane carbon dioxide electrolysis device: weighing MgRuPbSnOx0.8g of quaternary metal oxide catalyst, dispersed in 100 mL of ethanol, and 2mL of 5wt% Sustanion was added®A9 anion exchange membrane monomer solution, fully dispersed by ultrasonic. The catalyst slurry was sprayed using a spray gun to a thickness of 250 μm and an area of 200 cm2The titanium fiber paper gas diffusion electrode is weighed after being dried, and the operation is repeated until the loading capacity of the catalyst is 2 mg/cm2To obtain a supported catalystThe proton exchange membrane anode of (1).
(2) Preparing a cathode gas diffusion electrode of a proton exchange membrane electrolysis device: 0.4 g of nano-copper catalyst with the particle size of 40-60 nm is weighed and dispersed in ethanol, and 2.5mL of 5wt% Sustanion is added®A9 anion exchange membrane monomer solution, after fully ultrasonic dispersing, spraying the catalyst slurry on a Freudenburg H14C9 gas diffusion electrode with the thickness of 150 mu m, weighing after drying, repeating the operation until the copper loading of the catalyst is 3 mg/cm2. And drying to obtain the cathode gas diffusion electrode.
(3) An anion exchange membrane carbon dioxide electrolysis apparatus assembly: loading MgRuPbSnOxA titanium gas diffusion electrode (1) of the quaternary metal oxide catalyst and a carbon paper gas diffusion electrode (2) loaded with the nano-copper catalyst are respectively arranged on Sustanion®And hot-pressing both sides of the anion exchange membrane of 37-50 for 3 min at 130 ℃ and under the pressure of 2 Mpa to obtain the membrane electrode assembly for the anion exchange membrane carbon dioxide electrolysis device. Then, the titanium end plate (S-shaped flow channel, flow field area 25 cm)2) And seal rings and the like are sequentially assembled on both sides of the membrane electrode assembly (the structure is shown in fig. 14). And (3) fastening the end plates at two sides by using eight M6 hexagon socket head cap screws and matched hexagon nuts, wherein the fastening torsion is 0.6N/M, and then finishing the assembly of the anion exchange membrane carbon dioxide electrolysis device. Introducing 60 ℃ 1M KOH solution at one side of the anode, and applying voltage at two sides of the titanium flow field end plate to electrolyze carbon dioxide to prepare C1、C2Compounds (major products include carbon monoxide, ethylene, ethanol) and oxygen.

Claims (10)

1. An atom-level uniformly-dispersed ruthenium-based multi-element metal oxide material is prepared by a sol-gel method, Ru is used as a basic metal material, and a second metal A and a third metal M are introduced; is denoted as ARuMOx(ii) a Wherein, the atom percentage of Ru is 20-80%, the second element metal A is one of alkali metal and alkaline earth metal of Na, K, Mg, Ca, Sr and Ba, the atom percentage is 1-50%, the third element metal M is Ir, W, Pd, Mo, Ag, Mn transition metal or Pb, B,one or two of Sn, Sb and Si main group metals, the atomic percentage content of which is 15-70 percent; the sum of the atomic percentages of the three metal materials is 100 percent.
2. A method for preparing ruthenium-based multi-component metal oxide material according to claim 1, which adopts a sol-gel method, and is characterized by comprising the following steps:
(1) preparing a mixed solution of ruthenium-based metal salts: weighing 1-5 g of ruthenium salt, 0-2.5 g of alkaline earth metal salt and 1-5 g of transition metal salt or main group metal salt, dissolving in 50-200 mL of organic solvent, and placing the mixed solution in a refrigerator at-10-4 ℃ for 0-5 hours;
(2) adding an epoxy compound: slowly dripping 10-100 mL of epoxy compound and 1-20 mL of deionized water into the mixed solution at the speed of 0.5-50 mL/min, and stirring to fully mix;
(3) standing and precipitating: standing the mixed solution for 1-7 days to form jelly-like gel/precipitate in the solution, adding acetone, centrifuging to obtain precipitate, and washing the precipitate with acetone for 3-6 times; and drying;
(4) high-temperature calcination: the dried product is put into a tubular furnace, the temperature is raised to 400-800 ℃ at the temperature rise rate of 5-20 ℃/min in the air atmosphere, and the calcination is carried out for 0.5-6 hours to prepare the ruthenium-based multi-element metal oxide material ARuMOx。
3. The method according to claim 2, wherein the ruthenium salt is one of ruthenium trichloride hydrate, ruthenium trichloride trihydrate, anhydrous ruthenium trichloride, ruthenium acetylacetonate, and ruthenium nitrosyl nitrate.
4. The method according to claim 2, wherein the alkaline earth metal salt is 1 to 3 of Na, K, Mg, Ca, Sr, Ba hydrochloride, nitrate, sulfate, or acetate.
5. The method according to claim 2, wherein the transition metal or main group metal salt is 1 to 3 of Ir, W, Pd, Mo, Cu, Al, Ag, Mn, Pb, Sn, Sb, Si hydrochloride, nitrate, sulfate, acetate, perchlorate, or chlorate.
6. The method according to claim 2, wherein the organic solvent is one of methanol, ethanol, N-propanol, isopropanol, ethylene glycol, glycerol, acetone, N-dimethylformamide, N-dimethylhexanamide, dimethylsulfoxide, and tetrahydrofuran.
7. The method according to claim 2, wherein the epoxy compound is one of 1, 2-epoxypropane, 1, 2-epoxybutane, epichlorohydrin and epibromohydrin.
8. The application of the ruthenium-based multi-component metal oxide material as an electrode material of an electrochemical oxygen evolution reaction catalyst according to claim 1, which comprises the following steps:
dispersing a ruthenium-based multi-element metal oxide material and a conductive agent in a mixed solvent of an organic solvent and water, adding a binder, and coating catalyst slurry on a catalyst carrier after ultrasonic dispersion; after being dried, the anode is used as an anode for electrochemical oxygen evolution reaction;
wherein the conductive agent is carbon black, carbon nano tube and graphene, and the specific weight of the conductive agent is 10-30%; the adhesive is a 5% perfluorosulfonic acid polymer solution, and the specific gravity of the adhesive in the catalyst slurry is 5-30%; the catalyst carrier is carbon paper, carbon cloth, carbon felt, metal foam or metal foil, and the loading capacity of the catalyst is 2-50 mg/cm2(ii) a The organic solvent is methanol, ethanol, isopropanol, acetone or tetrahydrofuran.
9. Use of ruthenium-based multinary metal oxide material according to claim 1 as anode catalyst material in proton exchange membrane-based water electrolysis devices; the water electrolysis device based on the proton exchange membrane is assembled by taking the ruthenium-based multi-element metal oxide material as an anode catalyst, taking a platinum carbon catalyst with the platinum content of 20-100% as a cathode catalyst, taking a perfluorinated sulfonic acid resin proton exchange membrane with the thickness of 25-250 mu m as a diaphragm, taking carbon paper with a microporous layer and a porous sintered titanium plate as a cathode gas diffusion layer and an anode gas diffusion layer respectively, taking a titanium plate or a graphite plate with a carved flow field as a cathode end plate and an anode end plate, and introducing pure water or 0.05-2 mol/L sulfuric acid as electrolyte.
10. The use of the ruthenium-based polyvalent metal oxide material according to claim 1 as an electrode material for an electrochemical carbon dioxide reduction catalyst in an electrochemical carbon dioxide epoxidation facility; the carbon dioxide epoxy device takes a ruthenium-based multi-component metal oxide material as an anode catalyst and takes a copper, silver, gold or ruthenium-based multi-component metal oxide material as a cathode catalyst; an anion exchange membrane with the thickness of 25-250 mu m is taken as a diaphragm, carbon paper with a microporous layer and a porous sintered titanium plate are respectively taken as a cathode gas diffusion layer and an anode gas diffusion layer, a titanium plate or a graphite plate with a carved flow field is taken as a cathode end plate and an anode end plate, pure water or 0.05-10 mol/L potassium hydroxide solution is introduced as electrolyte, and the electrochemical carbon dioxide epoxy device is assembled.
CN202110379704.4A 2021-04-08 2021-04-08 Atom-level uniformly-dispersed ruthenium-based multi-element metal oxide material and preparation method and application thereof Pending CN113265681A (en)

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CN112877713A (en) * 2021-01-21 2021-06-01 徐军莲 Preparation method of composite nanosheet material of ruthenium oxide and strontium ruthenate based on perovskite structure
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