CN113026051A - Ruthenium-manganese oxide solid solution, preparation method thereof and application of ruthenium-manganese oxide solid solution as acidic oxygen precipitation reaction electrocatalyst - Google Patents
Ruthenium-manganese oxide solid solution, preparation method thereof and application of ruthenium-manganese oxide solid solution as acidic oxygen precipitation reaction electrocatalyst Download PDFInfo
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- XNUXYJSMIQDRDP-UHFFFAOYSA-N [O-2].[Mn+2].[Ru+3] Chemical compound [O-2].[Mn+2].[Ru+3] XNUXYJSMIQDRDP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000006104 solid solution Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 18
- 239000010411 electrocatalyst Substances 0.000 title claims description 25
- 230000002378 acidificating effect Effects 0.000 title claims description 19
- 238000001556 precipitation Methods 0.000 title abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 24
- 150000002696 manganese Chemical class 0.000 claims abstract description 23
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 229940058180 edetate dipotassium anhydrous Drugs 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 24
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000013522 chelant Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 13
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 10
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 10
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000005868 electrolysis reaction 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明提供了一种钌锰氧化物固溶体的制备方法，包括以下步骤：S1)将可溶性钌盐、可溶性锰盐与螯合剂在水中混合，然后调节混合液的pH值至弱酸性，加入醇溶剂，得到前驱体；S2)将所述前驱体在空气气氛中焙烧氧化，得到钌锰氧化物固溶体。与现有技术相比，本发明先制备出钌与锰均匀混合的螯合物前驱体，然后一步焙烧氧化即可得到空壳结构的钌锰氧化物固溶体，该制备方法简单，对生产设备要求低，原料易获得，有利于大规模生产，同时减少了贵金属的用量，降低了生产成本，并且得到的钌锰氧化物固溶体作为催化剂在酸性氧析出反应中活性高、寿命长，即使在较大电流密度下，仍具有较高的稳定性。The present invention provides a method for preparing a ruthenium manganese oxide solid solution, comprising the following steps: S1) mixing soluble ruthenium salt, soluble manganese salt and chelating agent in water, then adjusting the pH value of the mixed solution to weak acidity, adding alcohol solvent , to obtain a precursor; S2) roasting and oxidizing the precursor in an air atmosphere to obtain a ruthenium manganese oxide solid solution. Compared with the prior art, the present invention first prepares a chelate precursor in which ruthenium and manganese are uniformly mixed, and then one-step roasting and oxidation can obtain a ruthenium-manganese oxide solid solution with an empty shell structure. The preparation method is simple and requires production equipment. Low, easy to obtain raw materials, conducive to large-scale production, while reducing the amount of precious metals, reducing production costs, and the obtained ruthenium-manganese oxide solid solution as a catalyst in the acid oxygen precipitation reaction has high activity and long life, even in large Under the current density, it still has high stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a ruthenium-manganese oxide solid solution, a preparation method thereof and application of the ruthenium-manganese oxide solid solution as an acidic oxygen precipitation reaction electrocatalyst.
Background
The increasing global demand for energy doubles the demand of people for fossil energy such as coal, oil, natural gas and the like, but the toxic substances and carbon dioxide released by the combustion of the fossil energy cause environmental pollution and greenhouse effect in the global scope. To combat the growing environmental problems, various renewable energy technologies have been developed, such as wind, solar, tidal, etc. However, most of these renewable energy sources are intermittent and periodic, and how to store these renewable energy sources becomes a topic of concern.
The hydrogen production by electrolyzing water can convert the electric energy generated by wind energy, solar energy and the like into hydrogen to be stored, and the hydrogen is used as high-energy fuel, and the product of the reaction with oxygen is only water, so that the hydrogen production by electrolyzing water is a very attractive energy conversion mode. Compared with the electrolytic water reaction under the alkaline condition, the electrolytic water reaction under the acidic condition has higher mass transfer speed (the proton exchange membrane used under the acidic condition can reach 800-2500 mA cm under the working condition of 70-80 DEG C-2The anion exchange membrane used under the alkaline condition can only reach 200-500 mA cm under the working condition of 50-70 DEG C-2Current density) and higher product purity and efficiency, so that the development of the efficient water electrolysis reaction catalyst under acidic conditions has important large-scale application significance.
However, most known electrocatalysts are not capable of oxygen evolution under severe acidic conditions because at oxidation potential and acidic conditions the catalyst is readily soluble, resulting in loss of catalytic activity of the catalyst. Therefore, the development of an efficient and stable electrocatalyst for acidic oxygen evolution reactions is of great importance for the development of the electrolyzed water industry.
The existing oxygen evolution reaction catalysts used under acidic conditions are mainly iridium-based and ruthenium-based catalysts. Compared with the iridium-based catalyst, the ruthenium-based catalyst has the advantages of low price and high catalytic activity, but the ruthenium-based catalyst has poor anti-dissolution capability and short service life. Therefore, the development of ruthenium-based oxygen evolution catalysts with high activity, especially high stability, is the key to the development of water electrolysis under acidic conditions.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a ruthenium manganese oxide solid solution, a preparation method thereof, and an application thereof as an electrocatalyst for an acidic oxygen evolution reaction, wherein the ruthenium manganese oxide solid solution has high activity and stability in catalyzing the acidic oxygen evolution reaction.
The invention provides a preparation method of a ruthenium-manganese oxide solid solution, which comprises the following steps:
s1) mixing soluble ruthenium salt, soluble manganese salt and a chelating agent in water, then adjusting the pH value of the mixed solution to weak acidity, and adding an alcohol solvent to obtain a precursor;
s2) roasting and oxidizing the precursor in an air atmosphere to obtain the ruthenium-manganese oxide solid solution.
Preferably, the soluble ruthenium salt is selected from ruthenium chloride; the soluble manganese salt is selected from manganese chloride; the chelating agent is one or more of disodium ethylene diamine tetraacetate, dipotassium ethylene diamine tetraacetate and ethylene diamine tetraacetic acid; the alcohol solvent is selected from ethanol.
Preferably, the molar ratio of the soluble ruthenium salt to the soluble manganese salt is (1-9): (1-9); the mole number of the chelating agent is 40-60% of the total mole number of the soluble ruthenium salt and the soluble manganese salt.
Preferably, the molar ratio of the soluble ruthenium salt to the soluble manganese salt is (5-6): (4-5); the mole number of the chelating agent is 50% of the total mole number of the soluble ruthenium salt and the soluble manganese salt.
Preferably, the total molar concentration of the soluble ruthenium salt and the soluble manganese salt in the mixed solution is 0.1-0.3 mol/L.
Preferably, the pH value of the mixed solution is adjusted to 5-6 in the step S1); the volume ratio of the mixed solution to the alcohol solvent is 1: (3-5).
Preferably, the roasting oxidation temperature is 350-500 ℃; the roasting and oxidizing time is 1-5 h.
The invention also provides the ruthenium manganese oxide solid solution prepared by the preparation method.
Preferably, in the X-ray diffraction pattern of the ruthenium manganese oxide solid solution, the diffraction angle 2 theta has characteristic peaks at 28 +/-1, 36 +/-0.5, 41 +/-0.5, 55 +/-0.5, 66.5 +/-0.5 and 69 +/-0.5 degrees.
The invention also provides an acidic oxygen evolution reaction electrocatalyst which comprises the ruthenium-manganese oxide solid solution.
The invention provides a preparation method of a ruthenium-manganese oxide solid solution, which comprises the following steps: s1) mixing soluble ruthenium salt, soluble manganese salt and a chelating agent in water, then adjusting the pH value of the mixed solution to weak acidity, and adding an alcohol solvent to obtain a precursor; s2) roasting and oxidizing the precursor in an air atmosphere to obtain the ruthenium-manganese oxide solid solution. Compared with the prior art, the preparation method has the advantages that the chelate precursor with uniformly mixed ruthenium and manganese is prepared, and then the ruthenium-manganese oxide solid solution with a hollow shell structure can be obtained through one-step roasting and oxidation.
The experimental result shows that the current density of the ruthenium manganese oxide solid solution provided by the invention reaches 10mA/cm in the acidic oxygen precipitation reaction2When the overpotential is only 158mV, it can be set at 10mA/cm2The current density of the current is continuously operated for more than 500 hours.
Drawings
FIG. 1 is an X-ray diffraction pattern of a ruthenium manganese oxide solid solution electrocatalyst obtained in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a ruthenium manganese oxide solid solution electrocatalyst obtained in example 1 of the present invention;
FIG. 3 is a transmission electron micrograph of a ruthenium manganese oxide solid solution electrocatalyst obtained in example 1 of the present invention (transmission electron microscopy electron acceleration voltage is 100 kV);
FIG. 4 is a plot of the linear sweep voltammetry measurements of the ruthenium manganese oxide solid solution electrocatalyst obtained in example 1 of the present invention;
FIG. 5 shows the results of the present invention at 10mA/cm for the ruthenium manganese oxide solid solution electrocatalyst obtained in example 12、50mA/cm2And 100mA/cm2Current density ofConstant current test pattern below.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a ruthenium-manganese oxide solid solution, which comprises the following steps: s1) mixing soluble ruthenium salt, soluble manganese salt and a chelating agent in water, then adjusting the pH value of the mixed solution to weak acidity, and adding an alcohol solvent to obtain a precursor; s2) roasting and oxidizing the precursor in an air atmosphere to obtain the ruthenium-manganese oxide solid solution.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The soluble ruthenium salt is preferably ruthenium chloride; the soluble manganese salt is preferably manganese chloride; the chelating agent is preferably one or more of disodium ethylene diamine tetraacetate, dipotassium ethylene diamine tetraacetate and ethylene diamine tetraacetic acid.
Mixing soluble ruthenium salt, soluble manganese salt and chelating agent in water; the mol ratio of the soluble ruthenium salt to the soluble manganese salt is preferably (1-9): (1-9), more preferably (2-8): (2-8), and more preferably (3-7): (3-7), preferably (4-6): (4-6), most preferably (5-6): (4-5); the mole number of the chelating agent is preferably 40-60%, more preferably 45-55% and even more preferably 50% of the total mole number of the soluble ruthenium salt and the soluble manganese salt; in the present invention, it is preferable that the soluble ruthenium salt and the soluble manganese are dissolved in water first, and then the aqueous solution of the chelating agent is added; the total molar concentration of the soluble ruthenium salt and the soluble manganese salt in the mixed solution is preferably 0.1-0.3 mol/L, more preferably 0.15-0.25 mol/L, and further preferably 0.2-0.25 mol/L; in the embodiment provided by the invention, the total molar concentration of the soluble ruthenium salt and the soluble manganese salt in the mixed solution is specifically 0.22 mol/L.
Adjusting the pH value of the mixed solution to weak acidity, preferably adjusting the pH value to 5-6; in the present invention, ammonia is preferably used to adjust the pH of the mixed solution.
Then adding an alcohol solvent; the alcohol solvent is preferably ethanol; the volume ratio of the mixed solution to the alcohol solvent is preferably 1: (3-5), more preferably 1: (3.5-4.5), and preferably 1: 4; adding an alcohol solvent, preferably fully stirring, and separating precipitated solids to obtain a precursor; the separated solid is preferably washed with ethanol and then dried to obtain a precursor.
Roasting and oxidizing the precursor in an air atmosphere to obtain a ruthenium-manganese oxide solid solution; the roasting oxidation temperature is preferably 350-500 ℃, more preferably 400-450 ℃, and further preferably 400 ℃; the roasting oxidation time is preferably 1-5 h, more preferably 2-4 h, and further preferably 2-3 h.
According to the invention, the chelate precursor with uniformly mixed ruthenium and manganese is prepared, and then the ruthenium-manganese oxide solid solution with a hollow shell structure can be obtained by one-step roasting and oxidation.
The invention also provides a ruthenium manganese oxide solid solution prepared by the method; the ruthenium manganese oxide solid solution preferably has a hollow shell structure; in an X-ray diffraction spectrum of the ruthenium manganese oxide solid solution, characteristic peaks are preferably arranged at diffraction angles 2 theta of 28 +/-1, 36 +/-0.5, 41 +/-0.5, 55 +/-0.5, 66.5 +/-0.5 and 69 +/-0.5 degrees.
The invention also provides an acidic oxygen evolution reaction electrocatalyst which comprises the ruthenium-manganese oxide solid solution.
In the present invention, it is preferable to mix a ruthenium manganese oxide solid solution, ethanol, and a Nafion solution to obtain a catalyst slurry; coating the catalyst slurry on a current collector to obtain an anode for an electrolytic water precipitation reaction; the ratio of the mass of the ruthenium manganese oxide solid solution to the total volume of the ethanol and the Nafion solution is 1 mg: (25-30) μ l, more preferably 1 mg: 28 μ l; the volume ratio of the ethanol to the Nafion solution is preferably 25: (1-5), more preferably 25: 3; the concentration of the Nafion solution is preferably 3-8 wt%, and more preferably 5 wt%.
In order to further illustrate the present invention, the following will describe in detail a ruthenium manganese oxide solid solution, a method for preparing the same, and an application thereof as an acidic oxygen evolution reaction electrocatalyst, in accordance with the present invention, with reference to examples.
The reagents used in the following examples are all commercially available.
Example 1
(1) Preparation of the Mixed solution
First 129.3mg of RuCl3·3H2O and 98.5mg of MnCl2·4H2O was added to 2.5ml of water to form a salt solution. Then, 2.5ml of an aqueous solution of disodium ethylenediaminetetraacetate (186.24mg of disodium ethylenediaminetetraacetate dissolved in 2.5ml of water) was added to the above solution and sufficiently stirred. And finally, regulating the pH value of the mixed solution to be 5-6 by using concentrated ammonia water.
(2) Preparation of the precursor
And (2) adding 20ml of ethanol into the mixed solution in the step (1), and stirring and uniformly mixing. And collecting solids precipitated from the mixed solution, washing with ethanol, and then drying in vacuum to obtain a powdery precursor.
(3) One-step oxidation of precursor
And oxidizing the obtained precursor in air at 400 ℃ for 2h to obtain the ruthenium-manganese oxide solid solution electrocatalyst.
The ruthenium manganese oxide solid solution electrocatalyst obtained in example 1 was analyzed by X-ray diffraction, and its X-ray diffraction pattern was obtained, as shown in fig. 1.
The ruthenium manganese oxide solid solution electrocatalyst obtained in example 1 was analyzed by scanning electron microscopy, and a scanning electron microscopy image thereof was obtained as shown in fig. 2.
The ruthenium manganese oxide solid solution electrocatalyst obtained in example 1 was analyzed by transmission electron microscopy to obtain a transmission electron microscopy image, as shown in fig. 3.
(4) Evaluation of catalyst Performance
10mg of the ruthenium manganese oxide solid solution catalyst powder obtained in the step (3) was added to 280. mu.l of the mixed solution (containing 250. mu.l of anhydrous ethanol and 30. mu.l of 5 wt% Nafion) and stirred uniformly to prepare a catalyst slurry. Uniformly coating 40 mul of catalyst slurry on 0.6cm2The hydrophilic carbon paper is dried in the air and then used as an anode for electrolytic water oxygen precipitation reaction.
And (3) testing conditions are as follows: using a three electrode test method, carbon paper coated with catalyst as the working electrode, 0.5MH2SO4As electrolyte, Ag/AgCl was used as reference electrode, carbon rod as counter electrode, CHI760E as test instrument, and the test was performed at normal temperature and pressure.
Linear sweep voltammetry test: the voltage scanning range is 0.8-1.5V, and the scanning speed is 10 mV/s. The linear sweep voltammetry test pattern thereof was obtained as shown in fig. 4.
Constant current testing: current density 10mA/cm2. FIG. 5 shows the results of the ruthenium manganese oxide solid solution electrocatalyst at 10mA/cm obtained in example 12、50mA/cm2And 100mA/cm2Constant current test pattern at current density of (a).
Example 2
(1) Preparation of the Mixed solution
183.03mg of RuCl are first mixed3·3H2O and 59.37mg of MnCl2·4H2O was added to 2.5ml of water to form a salt solution. Then, 2.5ml of an aqueous solution of disodium ethylenediaminetetraacetate (186.24mg of disodium ethylenediaminetetraacetate dissolved in 2.5ml of water) was added to the above solution and sufficiently stirred. And finally, regulating the pH value of the mixed solution to be 5-6 by using concentrated ammonia water.
Steps (2) and (3) were the same as in example 1
(4) Evaluation of catalyst Performance
The same performance evaluation method as in example 1 was employed.
Example 3
Steps (1) and (2) were the same as in example 1
(3) One-step oxidation of precursor
And oxidizing the obtained precursor in air at 350 ℃ for 2h to obtain the ruthenium-manganese oxide solid solution electrocatalyst.
(4) Evaluation of catalyst Performance
The same performance evaluation method as in example 1 was employed.
Example 4
Steps (1) and (2) were the same as in example 1
(3) One-step oxidation of precursor
And oxidizing the obtained precursor in air at 450 ℃ for 2h to obtain the ruthenium-manganese oxide solid solution electrocatalyst.
(4) Evaluation of catalyst Performance
The same performance evaluation method as in example 1 was employed
Comparative example 1
Steps (1) and (2) were the same as in example 1
(3) One-step oxidation of precursor
And oxidizing the obtained precursor in air at 500 ℃ for 2h to obtain the ruthenium-manganese oxide solid solution electrocatalyst.
(4) Evaluation of catalyst Performance
The same performance evaluation method as in example 1 was employed.
Comparative example 2
(1) Preparation of the Mixed solution
13.07mg of RuCl was first added3·3H2O and 89.06mg of MnCl2·4H2O was added to 2.5ml of water to form a salt solution. Then, 2.5ml of an aqueous solution of disodium ethylenediaminetetraacetate (186.24mg of disodium ethylenediaminetetraacetate dissolved in 2.5ml of water) was added to the above solution and sufficiently stirred. And finally, regulating the pH value of the mixed solution to be 5-6 by using concentrated ammonia water.
Steps (2) and (3) were the same as in example 1
(4) Evaluation of catalyst Performance
The same performance evaluation method as in example 1 was employed.
Comparative example 3
(1) Preparation of the Mixed solution
First 78.44mg of RuCl3·3H2O and 138.53mg of MnCl2·4H2O was added to 2.5ml of water to form a salt solution. Then, 2.5ml of an aqueous solution of disodium ethylenediaminetetraacetate (186.24mg of disodium ethylenediaminetetraacetate dissolved in 2.5ml of water) was added to the above solution and sufficiently stirred. And finally, regulating the pH value of the mixed solution to be 5-6 by using concentrated ammonia water.
Steps (2) and (3) were the same as in example 1
(4) Evaluation of catalyst Performance
The same performance evaluation method as in example 1 was employed.
The performance of the catalysts obtained in examples 1 to 3 and comparative examples 1 to 2 was tested, and the results are shown in Table 1.
TABLE 1 results of catalyst Performance testing
| Catalyst and process for preparing same | 10mA/cm2Overpotential (mV) | 10mA/cm2Constant current stability test |
| Example 1 | 158 | Over 500 hours |
| Example 2 | 183 | Over 100 hours |
| Example 3 | 179 | Over 100 hours |
| Example 4 | 177 | Over 100 hours |
| Comparative example 1 | 221 | - |
| Comparative example 2 | 247 | - |
| Comparative example 3 | 187 | - |
As can be seen from table 1, the ruthenium manganese oxide solid solution electrocatalyst for acidic oxygen evolution reaction prepared by the method of example 1 of the present invention has small catalytic overpotential and excellent stability.
Claims (10)
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| CN114164440A (en) * | 2021-12-23 | 2022-03-11 | 南京大学 | A kind of preparation method of antimony-containing oxide catalyst for electrolysis of water under strong acid conditions |
| CN114250487A (en) * | 2021-12-17 | 2022-03-29 | 上海交通大学 | Carbon paper-supported ruthenium manganide catalyst and preparation method and application thereof |
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| CN114164440A (en) * | 2021-12-23 | 2022-03-11 | 南京大学 | A kind of preparation method of antimony-containing oxide catalyst for electrolysis of water under strong acid conditions |
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