CN116905016A - Preparation method and application of manganese-doped ruthenium dioxide coated ruthenium electrocatalyst - Google Patents
Preparation method and application of manganese-doped ruthenium dioxide coated ruthenium electrocatalyst Download PDFInfo
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 70
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 39
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 15
- 239000001103 potassium chloride Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/004—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method and application of a manganese-doped ruthenium dioxide coated ruthenium electrocatalyst, and relates to the technical field of electrocatalytic materials. The preparation method takes ruthenium trichloride solution and manganese acetylacetonate as raw materials, glucose as a reducing agent is dissolved in a water-alcohol mixed solvent, and the raw materials are subjected to hydrothermal treatment and then mixed with potassium chloride for heating. The manganese-doped ruthenium dioxide coated ruthenium electrocatalyst prepared by the invention has excellent catalytic activity and high stability, is expected to solve the problem of poor catalyst activity and stability in the current acidic medium, and is used as an anode of a PEM electrolytic tank of an industrial hydrogen evolution device.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to a preparation method and application of a manganese-doped ruthenium dioxide coated ruthenium electrocatalyst.
Background
Hydrogen is an important material that is an ideal energy carrier to overcome the current environmental and energy crisis. Electrolytic water hydrogen production is a green sustainable technology, but Oxygen Evolution Reaction (OER) of an anode is a complex process involving electron transfer proton coupling of four electrons, and the development of electrolytic water hydrogen production technology is limited due to a high reaction energy barrier. Therefore, an efficient oxygen evolution reaction electrocatalyst is needed to reduce the energy consumption of hydrogen production by water electrolysis.
The electrolyzed water can be realized under acidic, alkaline and neutral conditions, compared with the hydrogen ions under the acidic conditions, the conductivity of the hydrogen ions is far higher than that of the hydroxyl ions, the energy transmission is more facilitated, meanwhile, the proton concentration Gao Huiyou is faster than that of Hydrogen Evolution Reaction (HER) under the alkaline conditions, and the advantages of higher product purity, higher efficiency and the like are also realized. Proton Exchange Membrane (PEM) cells in acidic media offer greater advantages over alkaline cells, such as greater power density, higher gas purity, greater load range, wider operating temperatures, and smaller cell area, so PEM cells in acidic media have wide prospects for development.
Ruthenium-based and iridium-based noble metals are currently the best electrocatalysts for PEM electrolyzer anode oxygen evolution reactions, but long-term studies have found that noble metal ruthenium-based has the advantage of higher activity and cheaper price than noble metal iridium-based, but ruthenium-based catalysts are easily dissolved by oxidation in acidic media. Therefore, the development of a ruthenium-based electrocatalyst with high catalytic activity, which stably operates in an acidic environment, is a key point and a difficulty of the industry of producing hydrogen by electrolysis of water.
Disclosure of Invention
The invention aims to provide a preparation method and application of a manganese-doped ruthenium dioxide coated ruthenium electrocatalyst, and the prepared manganese-doped ruthenium dioxide coated ruthenium electrocatalyst has high electrode activity and good stability and can be used as an anode of an acidic water electrolysis hydrogen production device.
In order to achieve the above purpose, the invention provides a preparation method of a manganese doped ruthenium dioxide coated ruthenium electrocatalyst, comprising the following steps:
s1, respectively weighing a certain amount of manganese acetylacetonate and glucose, adding the manganese acetylacetonate and the glucose into an alcohol-water mixed solution, adding a certain amount of ruthenium trichloride aqueous solution, fully dissolving and mixing by ultrasound, and then placing the mixture into a reaction kettle to heat for 2-24 hours at 150-180 ℃ to obtain a solid A;
s2, cleaning the solid A by using an alcohol-water mixed solution, and then putting the solid A into an oven to be dried at 65 ℃ to obtain a solid B;
s3, adding the solid B and potassium chloride into deionized water, carrying out ultrasonic treatment until the potassium chloride is fully dissolved, and then putting the mixture into an oven to be dried for 12 hours at 65 ℃ to obtain a solid C;
s4, grinding the solid C, uniformly grinding, then placing the ground solid C into a muffle furnace, and heating the ground solid C in an air atmosphere to obtain a solid D;
s5, washing the solid D with deionized water, and then putting the solid D into an oven to be dried at 65 ℃ to obtain the target product catalyst.
Preferably, in the step S1, the molar ratio of the manganese acetylacetonate to the ruthenium trichloride is 0.8-1.2.
Preferably, in the step S1, the volume ratio of the alcohol to the water in the alcohol-water mixed solution is 5:2.
Preferably, in the step S2, the volume ratio of the alcohol to the water in the alcohol-water mixed solution is 3:1.
Preferably, the mass of the potassium chloride in the step S3 is 0-100 times of the mass of the solid B.
Preferably, in the step S3, the mass of potassium chloride is 10 times that of the solid B.
Preferably, the heating temperature in the step S4 is 200-400 ℃, the reaction time is 2-8h, and the heating rate is 1 ℃/min.
Preferably, the heating temperature in the step S4 is 300 ℃, and the reaction time is 8 hours.
The manganese doped ruthenium dioxide coated ruthenium electrocatalyst prepared by the preparation method is used as an anode in an electrolytic water hydrogen evolution device.
Therefore, the invention provides a preparation method and application of the manganese-doped ruthenium dioxide coated ruthenium electrocatalyst, and the preparation method has the following specific beneficial effects:
(1) The method for preparing the catalyst by coating ruthenium with manganese-doped ruthenium dioxide reduces the use of noble metals and the preparation cost of the catalyst;
(2) The preparation method disclosed by the invention is simple in process and convenient to operate;
(3) The manganese-doped ruthenium dioxide coated ruthenium electrocatalyst prepared by the method has high electrode activity and good stability, and can be used as an anode of an acidic water electrolysis hydrogen production device; the electrocatalyst reaches 10mA/cm in an acidic medium with a pH of approximately 0.3 2 The current density of (C) is in the range of 185-220 mV and at 10mA/cm 2 The stable operation time under the current density condition exceeds 220 hours, and the over-potential rising rate is only 0.15-0.16 mV/h.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a graph showing the polarization of the Mn-doped ruthenium dioxide coated ruthenium electrocatalyst and commercial ruthenium oxide prepared in examples 1-3, respectively, of the present invention as an anode in an electrode system;
FIG. 2 is a graph of 10mA/cm for a manganese doped ruthenium dioxide coated ruthenium electrocatalyst prepared according to each of examples 1-3 of the invention and for commercial ruthenium oxide as anode in an electrode system 2 Voltage-time diagram of (2);
FIG. 3 is an X-ray diffraction pattern of a manganese doped ruthenium dioxide coated ruthenium electrocatalyst powder prepared according to example 1 of the invention;
FIG. 4 is a high power transmission electron microscope image of the ruthenium-coated manganese-doped ruthenium dioxide electrocatalyst prepared in example 1 of the invention;
FIG. 5 is an EDS linear scan of a ruthenium-coated manganese-doped ruthenium dioxide electrocatalyst prepared in example 1 of the invention.
Detailed Description
The following detailed description of the embodiments of the invention, provided in the accompanying drawings, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention provides a preparation method of a manganese-doped ruthenium dioxide coated ruthenium electrocatalyst, which comprises the following steps:
s1, respectively weighing 100.7mg of manganese acetylacetonate and 20mg of glucose, adding into 28mL of alcohol-water (volume ratio is 5:2) mixed solution, adding 10mL of 0.5M ruthenium trichloride aqueous solution, fully dissolving and mixing by ultrasonic for 30min, and then placing into a reaction kettle and heating for 2h at 180 ℃ to obtain a solid A;
s2, washing the solid A with an alcohol-water (volume ratio is 3:1) mixed solution for 2-3 times to wash out impurities such as residual organic matters, and then drying in an oven at 65 ℃ to obtain a solid B;
s3, adding the solid B and potassium chloride (the mass ratio is 1:10) into 5mL of deionized water, carrying out ultrasonic treatment for 30min until the potassium chloride is fully dissolved, and then putting the mixture into an oven to be dried for 12 hours at 65 ℃ to obtain a solid C;
s4, grinding the solid C, uniformly grinding, then placing the ground solid C into a muffle furnace, and heating the ground solid C in an air atmosphere at 300 ℃ for 8 hours to obtain a solid D, wherein the heating rate is 1 ℃/min;
s5, washing the solid D with deionized water, and then putting the solid D into an oven to be dried at 65 ℃ to obtain the target product catalyst.
Example 2
The invention provides a preparation method of a manganese-doped ruthenium dioxide coated ruthenium electrocatalyst, which comprises the following steps:
s1, respectively weighing 100.7mg of manganese acetylacetonate and 20mg of glucose, adding into 28mL of alcohol-water (volume ratio is 5:2) mixed solution, adding 10mL of 0.5M ruthenium trichloride aqueous solution, fully dissolving and mixing by ultrasonic for 30min, and then placing into a reaction kettle and heating for 2h at 180 ℃ to obtain a solid A;
s2, washing the solid A with an alcohol-water (volume ratio is 3:1) mixed solution for 2-3 times to wash out impurities such as residual organic matters, and then drying in an oven at 65 ℃ to obtain a solid B;
s3, adding the solid B and potassium chloride (the mass ratio is 1:10) into 5mL of deionized water, carrying out ultrasonic treatment for 30min until the potassium chloride is fully dissolved, and then putting the mixture into an oven to be dried for 12 hours at 65 ℃ to obtain a solid C;
s4, grinding the solid C, uniformly grinding, then placing the ground solid C into a muffle furnace, and heating the ground solid C in an air atmosphere at 200 ℃ for 8 hours to obtain a solid D, wherein the heating rate is 1 ℃/min;
s5, washing the solid D with deionized water, and then putting the solid D into an oven to be dried at 65 ℃ to obtain the target product catalyst.
Example 3
The invention provides a preparation method of a manganese-doped ruthenium dioxide coated ruthenium electrocatalyst, which comprises the following steps:
s1, respectively weighing 100.7mg of manganese acetylacetonate and 20mg of glucose, adding into 28mL of alcohol-water (volume ratio is 5:2) mixed solution, adding 10mL of 0.5M ruthenium trichloride aqueous solution, fully dissolving and mixing by ultrasonic for 30min, and then placing into a reaction kettle and heating for 2h at 180 ℃ to obtain a solid A;
s2, washing the solid A with an alcohol-water (volume ratio is 3:1) mixed solution for 2-3 times to wash out impurities such as residual organic matters, and then drying in an oven at 65 ℃ to obtain a solid B;
s3, adding the solid B and potassium chloride (the mass ratio is 1:10) into 5mL of deionized water, carrying out ultrasonic treatment for 30min until the potassium chloride is fully dissolved, and then putting the mixture into an oven to be dried for 12 hours at 65 ℃ to obtain a solid C;
s4, grinding the solid C, uniformly grinding, then placing the ground solid C into a muffle furnace, and heating the ground solid C at 400 ℃ in an air atmosphere for 8 hours to obtain a solid D, wherein the heating rate is 1 ℃/min;
s5, washing the solid D with deionized water, and then putting the solid D into an oven to be dried at 65 ℃ to obtain the target product catalyst.
As can be seen from FIG. 1, the catalyst reached 10mA/cm in an acidic medium having a pH of approximately 0.3 2 The current density of (2) is 185-220 mV, only small energy is needed to catalyze the reaction in the water electrolysis process, and the 300 ℃ annealing performance is best.
As can be seen from FIG. 2, the catalyst has good stability at 300 ℃ and can work for more than 200 hours at a current density of 10 milliamperes per square centimeter for a long time.
As can be seen from fig. 3, two phases of ruthenium and ruthenium oxide exist mainly in the catalyst.
As can be seen from fig. 4, the nanoparticles of the catalyst are small, about 5 to 8nm.
As can be seen from fig. 5, the catalyst is in a state where the inner layer is metallic ruthenium and the outer layer is ruthenium oxide.
The acid oxygen evolution performance test was performed using the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst prepared in examples 1 to 3 above.
The manganese-doped ruthenium dioxide coated ruthenium electrocatalyst prepared in examples 1-3 was used as an anode directly, respectively, using a three-electrode system; the reference electrode is an Ag/AgCl electrode; the counter electrode is a platinum mesh and a graphite electrode. The electrolyte solution was a 0.5M sulfuric acid solution. Potential reference Reversible Hydrogen Electrode (RHE): e (E) RHE ＝E Ag/AgCl +0.098+0.05926×pH(0.5MH 2 SO 4 A solution). The overpotential (η) is calculated according to the following equation: η=e RHE -1.23V. At a scan rate of 10mV/s at 0.5MH 2 SO 4 Linear Sweep Voltammetry (LSV) was recorded in solution to obtain a polarization curve, with all electrode potential data being compensated for 85% voltage drop.
Therefore, the invention provides a preparation method and application of the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst, and the method for preparing the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst reduces the use of noble metals and reduces the preparation cost of the catalyst; the preparation method is simple in process and convenient to operate; the catalyst reaches 10mA/cm in an acidic medium with pH of about 0.3 2 The current density of (C) is in the range of 185-220 mV and at 10mA/cm 2 The stable operation time under the current density condition exceeds 220 hours, and the over-potential rising rate is only 0.15-0.16 mV/h. The electrode has high activity and good stability, and can be used as an anode of an acidic water electrolysis hydrogen production device.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (9)
1. The preparation method of the manganese-doped ruthenium dioxide coated ruthenium electrocatalyst is characterized by comprising the following steps of:
s1, respectively weighing a certain amount of manganese acetylacetonate and glucose, adding the manganese acetylacetonate and the glucose into an alcohol-water mixed solution, adding a certain amount of ruthenium trichloride aqueous solution, fully dissolving and mixing by ultrasound, and then placing the mixture into a reaction kettle to heat for 2-24 hours at 150-180 ℃ to obtain a solid A;
s2, cleaning the solid A by using an alcohol-water mixed solution, and then putting the solid A into an oven to be dried at 65 ℃ to obtain a solid B;
s3, adding the solid B and potassium chloride into deionized water, carrying out ultrasonic treatment until the potassium chloride is fully dissolved, and then putting the mixture into an oven to be dried for 12 hours at 65 ℃ to obtain a solid C;
s4, grinding the solid C, uniformly grinding, then placing the ground solid C into a muffle furnace, and heating the ground solid C in an air atmosphere to obtain a solid D;
s5, washing the solid D with deionized water, and then putting the solid D into an oven to be dried at 65 ℃ to obtain the target product catalyst.
2. The method for preparing the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst according to claim 1, wherein the method comprises the following steps: the molar ratio of the manganese acetylacetonate to the ruthenium trichloride in the step S1 is 0.8-1.2.
3. The method for preparing the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst according to claim 1, wherein the method comprises the following steps: in the step S1, the volume ratio of alcohol to water in the alcohol-water mixed solution is 5:2.
4. The method for preparing the manganese-doped ruthenium dioxide coated ruthenium electrocatalyst according to claim 1, wherein the volume ratio of alcohol to water in the alcohol-water mixed solution in step S2 is 3:1.
5. The method for preparing the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst according to claim 1, wherein the method comprises the following steps: the mass of the potassium chloride in the step S3 is 0-100 times of that of the solid B.
6. The method for preparing the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst according to claim 5, wherein the method comprises the following steps: the mass of the potassium chloride in the step S3 is 10 times of that of the solid B.
7. The method for preparing the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst according to claim 1, wherein the method comprises the following steps: the heating temperature in the step S4 is 200-400 ℃, the reaction time is 2-8h, and the heating rate is 1 ℃/min.
8. The method for preparing the manganese-doped ruthenium dioxide-coated ruthenium electrocatalyst according to claim 7, wherein the method comprises the following steps: the heating temperature in the step S4 is 300 ℃, and the reaction time is 8 hours.
9. Use of the manganese doped ruthenium dioxide coated ruthenium electrocatalyst prepared by the method according to any one of claims 1 to 4 as an anode in an electrolyzed water hydrogen evolution apparatus.
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