CN117174920A - Preparation method and application of heterostructure ruthenium cobalt boron-based oxide catalyst - Google Patents
Preparation method and application of heterostructure ruthenium cobalt boron-based oxide catalyst Download PDFInfo
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- CN117174920A CN117174920A CN202310985351.1A CN202310985351A CN117174920A CN 117174920 A CN117174920 A CN 117174920A CN 202310985351 A CN202310985351 A CN 202310985351A CN 117174920 A CN117174920 A CN 117174920A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- XGLHOUMWRDNHHX-UHFFFAOYSA-N [Ru].[B].[Co] Chemical compound [Ru].[B].[Co] XGLHOUMWRDNHHX-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910020674 Co—B Inorganic materials 0.000 claims abstract description 75
- 239000000446 fuel Substances 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 150000001868 cobalt Chemical class 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 36
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 229910052700 potassium Inorganic materials 0.000 claims description 27
- 239000011591 potassium Substances 0.000 claims description 27
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910002848 Pt–Ru Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WAUIPKMDSHEJSA-UHFFFAOYSA-N copper palladium platinum Chemical compound [Cu][Pd][Pt] WAUIPKMDSHEJSA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- Y02E60/50—Fuel cells
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- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts and preparation thereof, and relates to a preparation method and application of a heterostructure ruthenium cobalt boron-based oxide catalyst, wherein the preparation method comprises the following steps: 1) Preparing a Co-B precursor: respectively weighing cobalt salt and borohydride according to the molar ratio of cobalt element to boron element of 1:2, and obtaining a Co-B precursor through dissolving, stirring, precipitating, separating and drying; 2) Preparation of Ru-Co-B based oxide catalyst: according to the mol ratio of ruthenium element to cobalt element of 1 (4-16), respectively weighing ruthenium salt and Co-B precursor, and carrying out mixed grinding and plasma technology treatment to obtain the Ru-Co-B based oxide catalyst. The preparation method of the heterostructure ruthenium cobalt boron-based oxide catalyst by utilizing the plasma technology is simple, easy to operate and capable of being prepared in a large scale; the prepared catalyst has high activity and can improve the discharge performance of the battery when used in a fuel cell.
Description
Technical Field
The invention belongs to the technical field of catalysts and preparation thereof, and relates to a preparation method and application of a heterostructure ruthenium cobalt boron-based oxide catalyst.
Background
The fuel cell is a high-efficiency clean electrochemical generating device for converting chemical energy of fuel such as hydrogen, methanol, ethanol, hydrocarbon, borohydride and the like into electric energy, and has the advantages of high efficiency, environmental friendliness and the like. Fuel cells are considered to be the most promising energy conversion strategy for achieving sustainable development of energy.
At present, fuel cell technology has been greatly developed, however, since most of the catalysts are composed of noble metals, especially Pt metals, the large-scale application of fuel cells is still limited due to the problems of high price, limited reserves of noble metals and the like. On the way of commercialization of low-temperature fuel cells such as Proton Exchange Membrane Fuel Cells (PEMFC), methanol fuel cells (DMFC), and borohydride fuel cells (DBFC), durability and cost of fuel cells are two major challenges of whether fuel cells can be developed and commercialized for a long time, so that by reducing the noble metal content in an electrode assembly, the cost of the cells can be directly reduced, but the cell performance and long-term stability are affected due to the reduction of the content.
In recent years, catalyst cost is reduced and catalyst performance is improved mainly by the following two ways: (1) developing a platinum alloy catalyst; (2) development of non-platinum electrocatalysts; while the above approach can achieve cost and performance advantages, the following problems exist: currently, for the synthesis of such fuel cell catalysts, mainly conventional chemical synthesis methods or high temperature treatments are adopted, for example, document Molten salt assisted to synthesize molybdenume ruthenium boride for hydrogen generation in wide pH range mentions that molybdenum pentachloride, sodium chloride, potassium chloride, amorphous boron powder and ruthenium trichloride are mixed together by a melting method, ground until they become powder, then the above powder is placed in a tube furnace, and after heating, the obtained nanomaterial Mo-Ru-B is obtained. Document Ultrafine amorphous Co-W-B alloy as the anode catalyst for a direct borohydride fuThe superfine amorphous Co-W-B alloy is prepared by adopting a chemical reduction method in the el cell. By chemical reduction of cobalt chloride (CoCl) with potassium borohydride solution 2 ) And sodium tungstate (Na) 2 WO 4 ) And (5) synthesizing. To CoCl of different volumes 2 And Na (Na) 2 WO 4 The solutions were mixed together to adjust the tungsten content of the sample. KBH was then stirred magnetically 4 Dropwise adding KOH solution into the mixed solution, adding potassium borohydride to release hydrogen, stirring to obtain black precipitate, filtering and washing with distilled water to obtain Co-W-B; patent CN 105702971A describes a core-shell gold@cobalt-boron catalyst for fuel cells. Preparing a mixed solution of cobalt salt and gold salt, dissolving borohydride in deionized water to prepare a borohydride solution, adding hydroxide into the borohydride solution, adding the borohydride-hydroxide mixed solution into the mixed solution of cobalt salt and gold salt at a certain speed, and continuously stirring and filtering the reaction material to obtain a precipitate after no gas is generated in the reaction, thus obtaining the core-shell type gold@cobalt-boron catalyst. Patent CN201210120922.7 describes a carbon-supported core-shell type copper-palladium-platinum catalyst for fuel cells and a preparation method thereof. The method adopts a two-step reduction method, namely, firstly reducing low-activity metal and then reducing active noble metal, and the noble metal is deposited on the surface of non-noble metal by controlling the temperature and the pH value of the reaction, and the dealloying step is assisted, so that the core-shell catalyst is prepared.
The methods have the problems of complex synthesis process, high energy consumption and difficult realization of large-scale production in the long term.
Disclosure of Invention
The invention provides a preparation method and application of a heterostructure ruthenium cobalt boron-based oxide catalyst, aiming at solving the technical problem that the existing fuel cell catalyst has a complex synthesis process.
In order to achieve the purpose, the method for preparing the heterostructure ruthenium cobalt boron-based oxide catalyst by utilizing the plasma technology is simple, easy to operate and capable of being prepared on a large scale; the prepared catalyst has high activity and can improve the discharge performance of the battery when used in a fuel cell. The technical scheme adopted by the invention is as follows:
the preparation method of the heterostructure ruthenium cobalt boron-based oxide catalyst is characterized by comprising the following steps of:
1) Preparation of Co-B precursor
Respectively weighing cobalt salt and borohydride according to the molar ratio of cobalt element to boron element of 1:2, and obtaining a Co-B precursor through dissolving, stirring, precipitating, separating and drying;
2) Preparation of Ru-Co-B based oxide catalyst
And (4) respectively weighing ruthenium salt and Co-B precursor according to the mol ratio of ruthenium element to cobalt element of 1 (4-16), and carrying out mixed grinding and plasma technology treatment to obtain the Ru-Co-B catalyst.
Further defined, in said step 2), the conditions of the plasma technical treatment are: the voltage is 40V-70V, the treatment time is 5min-20min, and the temperature is normal temperature.
Further defined, in the step 2), the ruthenium salt is anhydrous ruthenium trichloride.
Further defined, the step 1) specifically includes the following steps:
1.1 Dissolving the weighed cobalt salt in water to obtain a cobalt salt solution;
1.2 Dissolving the weighed borohydride in water to obtain a borohydride solution;
1.3 Dropwise adding the borohydride solution into the cobalt salt solution, stirring until the reaction is complete, and obtaining the Co-B precursor through standing precipitation, filtering separation and drying.
Further defined, in the step 1.1), the cobalt salt is cobalt chloride hexahydrate, and the concentration of the cobalt salt solution is 0.015mol/L.
Further defined, in the step 1.2), the borohydride is potassium borohydride, and the concentration of the potassium borohydride solution is 0.03mol/L.
Further defined, in the step 1.3), the dropping speed is 1 mL/min-2 mL/min; the drying conditions are as follows: vacuum degree is 80Pa-100Pa, temperature is 60 ℃ to 120 ℃ and time is 6h-12h.
The ruthenium cobalt boron-based oxide catalyst prepared by the preparation method of the heterostructure ruthenium cobalt boron-based oxide catalyst is a core-shell-sheet mosaic heterostructure.
The application of the ruthenium cobalt boron-based oxide catalyst as an anode catalyst in a borohydride fuel cell.
Further defined, the borohydride fuel cell has a maximum power density of 143.12mW cm -2 ～206.35mW·cm -2 。
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional chemical synthesis method, the method is simple, easy to operate and realizes large-scale production.
2. The invention adopts low temperature plasma technology, the temperature is normal temperature, and compared with the high temperature treatment in the traditional chemical method, the energy consumption is reduced.
3. According to the preparation method provided by the invention, reactants are fully ground and uniformly mixed, then a low-temperature plasma technology is adopted to generate a high-voltage electric field, and the reactants are bombarded into ions, atoms or free radicals and other particles under the action of the high-voltage electric field, so that the structure of the reactants is changed, a core-shell-sheet embedded heterostructure is shown, and the prepared catalyst is assembled in a battery, so that the performance of the catalyst can be greatly improved, and the excellent electrochemical performance is realized.
4. The ruthenium cobalt boron-based oxide catalyst prepared by the invention is a core-shell-sheet mosaic heterostructure, and compared with a spherical, core-shell structure or hollow structure reported in the prior literature, the catalyst of the structure has low cost and high activity; cerium oxide on carbon (CeO) 2 and/C) is a direct borohydride fuel cell DBFC cathode catalyst, ru-Co-B is a fuel cell assembled by anode catalyst, and the maximum power density of the fuel cell is up to 143.12mW cm -2 ～206.35mW·cm -2 The discharge performance of the fuel cell is better.
4. The catalyst prepared by the invention consists of ruthenium, cobalt and boron, the molar ratio of ruthenium element, cobalt element and boron element is 1 (4-16) (8-32), the molar fraction of ruthenium element is 9.09%, the use level of noble metal is greatly reduced, the content of platinum in the platinum-based catalyst with excellent characteristics is about 10%, the cost of ruthenium is the lowest in platinum group metal, the price is far lower than that of platinum, the cost of the fuel cell is obviously reduced, and the catalyst is favorable for promoting the development of the fuel cell.
Drawings
FIG. 1 is a scanning electron microscope image at a magnification of 150000 times of the Ru-Co-B based oxide catalyst prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the Ru-Co-B based oxide catalyst prepared according to example 1 of the present invention at 50000 times magnification;
FIG. 3 is a scanning electron microscope image of the Ru-Co-B based oxide catalyst prepared according to example 1 of the present invention at 200000 times magnification;
FIG. 4 is a scanning electron microscope image of the Ru-Co-B based oxide catalyst prepared according to example 1 of the present invention at 100000 magnification;
FIG. 5 is an EDS spectrum of a Ru-Co-B based oxide catalyst prepared according to example 1 of the present invention;
FIG. 6 is an XRD spectrum of Ru-Co-B based oxide catalysts prepared according to examples 1 to 4 of the present invention;
FIG. 7 is a graph showing the power performance of the Ru-Co-B based oxide catalyst prepared according to example 1 of the present invention as a direct borohydride fuel cell anode catalyst versus the cell performance of commercial Pt-Ru/C, commercial Pt/C, chemically prepared Ru-Co-B and CoB catalysts as direct borohydride fuel cell anodes, respectively;
FIG. 8 shows a constant current discharge test of the Ru-Co-B based oxide catalyst prepared according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is now described in detail with reference to the accompanying drawings and examples.
A preparation method of a heterostructure ruthenium cobalt boron-based oxide catalyst comprises the following steps.
1) Preparation of Co-B precursor
Cobalt salt and borohydride are respectively weighed according to the mol ratio of cobalt element to boron element of 1:2, and the Co-B precursor is obtained through dissolution, stirring, precipitation, separation and drying.
The Co-B precursor comprises the following steps:
1.1 Dissolving the weighed cobalt salt in water to obtain a cobalt salt solution.
Preferably, the cobalt salt is cobalt chloride hexahydrate, but anhydrous cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, etc. may also be used, and the concentration of the cobalt salt solution is 0.015mol/L.
1.2 Dissolving the weighed borohydride in water to obtain a borohydride solution.
Preferably, the borohydride is potassium borohydride, but sodium borohydride, lithium borohydride, etc. may also be used, wherein the concentration of the borohydride solution is 0.03mol/L.
1.3 Dropwise adding the borohydride solution into the cobalt salt solution, stirring until the reaction is complete, and obtaining the Co-B precursor through standing precipitation, filtering separation and drying.
In the step, the dropping speed is 1 mL/min-2 mL/min; the drying conditions are as follows: vacuum degree is 80Pa-100Pa, temperature is 60 ℃ to 120 ℃ and time is 6h-12h.
2) Preparation of Ru-Co-B based oxide catalyst
According to the mol ratio of ruthenium element to cobalt element of 1 (4-16), respectively weighing ruthenium salt and Co-B precursor, and carrying out mixed grinding and plasma technology treatment to obtain the Ru-Co-B based oxide catalyst.
Specifically, the molar ratio of the ruthenium salt is deduced reversely according to the molar ratio of cobalt element to boron element in the Co-B precursor of 1:2, and the amount of the prepared cobalt salt substance is standard.
In this step, the conditions for the plasma treatment are: the voltage is 40V-70V, the treatment time is 5min-20min, and the temperature is normal temperature.
Preferably, the ruthenium salt is anhydrous ruthenium trichloride, but water-soluble ruthenium trichloride (RuCl) may also be selected as the ruthenium salt 3 ·xH 2 O), ruthenium nitrate, ruthenium sulfate, ruthenium acetate, and the like.
The ruthenium cobalt boron-based oxide catalyst prepared by the method is of a core-shell-sheet embedded heterostructure, can be used as an anode catalyst in a borohydride fuel cell, and is prepared by CeO 2 and/C is the cathode catalyst, maximum power density of the assembled fuel cellIs 143.12mW cm -2 ～206.35mW·cm -2 The discharge performance is better.
The preparation process according to the invention and the performance advantages of the catalyst are illustrated in the following in several specific examples.
Example 1
The preparation method of the heterostructure ruthenium cobalt boron-based oxide catalyst in the embodiment comprises the following steps.
1) Preparation of Co-B precursor
1.1 Preparing a cobalt salt solution: 0.9137g of cobalt chloride hexahydrate is weighed and dissolved in deionized water, and the volume is fixed to a 250mL volumetric flask to obtain a cobalt chloride hexahydrate solution with the concentration of 0.015mol/L.
1.2 Preparation of potassium borohydride solution: according to the standard that the molar ratio of cobalt element to boron element is 1:2, 0.4142g of potassium borohydride is weighed, the potassium borohydride is dissolved in deionized water, and the volume is fixed to a 250mL volumetric flask, so that a potassium borohydride solution with the concentration of 0.03mol/L is prepared.
1.3 Preparing a Co-B precursor: slowly dripping 0.03mol/L and 250mL of potassium borohydride solution into 0.015mol/L and 250mL of cobalt chloride hexahydrate solution, stirring continuously, completely reacting after no bubble emerges, standing for half an hour, filtering, and drying in a vacuum drying oven with the vacuum degree of 80Pa and the temperature of 60 ℃ for 12 hours to finally obtain the Co-B precursor.
2) Preparation of Ru-Co-B based oxide catalyst
Weighing 0.1g of anhydrous ruthenium trichloride according to the standard that the molar ratio of ruthenium element to cobalt element is 1:8; and weighing 0.1g of the Co-B precursor according to the standard that the mass ratio of the Co-B precursor to the anhydrous ruthenium trichloride is 1:1, mixing the precursor with the weighed anhydrous ruthenium trichloride, fully grinding, then placing the mixed solid particles into a low-temperature plasma device, and carrying out electrifying treatment for 10min under the voltage of 50V in an air state atmosphere to finally obtain the Ru-Co-B catalyst.
In this embodiment, the positive electrode and the negative electrode of the low-temperature plasma device are made of conductive metal materials such as stainless steel, copper, aluminum, iron and the like.
The Ru-Co-B-based oxide catalyst prepared in this example was characterized.
1. SEM scans of the catalyst at different magnification are 150000-fold, 50000-fold, 200000-fold and 100000-fold, respectively, as shown in fig. 1-4.
The SEM scanning was performed with a scanning electron microscope Hitachi SU8230, cold field emission in a transition cabin, and vacuum.
As can be seen from fig. 1 to 4, the Ru-Co-B based oxide synthesized according to example 1 is core-shell-lamellar mosaic, and has a uniform morphology, which is nano-scale. Therefore, the catalyst prepared by adopting the plasma technology is a nano catalyst with a heterostructure, and is different from the load and wrapping structure prepared by the prior method, and the structure is greatly changed, and the performance of the catalyst is greatly improved and improved due to the core-shell-sheet embedded heterostructure, so that the catalyst is remarkably superior to the catalyst prepared by the conventional method.
2. EDS energy spectrum
The instrument used for EDS was FEI Talos F200x, usa, and was tested under vacuum by bombardment with electron beams.
The distribution of the three elements Ru, co and B can be seen from the graph of FIG. 5, and the three elements are well doped together.
3. XRD spectrum
XRD was performed using a RIGAKU SMARTLAB diffractometer under a scanning angle in the range of 10 DEG to 80 DEG and a scanning speed of 10 DEG/min.
As can be seen from FIG. 6, XRD patterns of Ru-Co-B based oxides with different molar ratios are shown as CoO and RuO when 2θ=35°, respectively 2 、B 20 H 26 The three substances form a heterostructure, and diffraction peaks of Co, ru and B are respectively consistent with standard peaks (JCPDS No.42-1300, JCPDS No.43-1027 and JCPDS No. 22-0118), which shows that the catalyst of the Ru-Co-B based oxide heterostructure is successfully prepared after the plasma effect.
4. Cell performance
Ru-Co-B based oxide prepared in the embodiment is used as anode catalyst of DBFC of borohydride fuel cell, and CeO 2 The discharge performance of a single DBFC is tested by a cell test system (from Shenshen Neware Technology Limited in China), oxygen is introduced at room temperature for testing, and the maximum power density of the fuel cell is 143.12 mW.cm -2 。
Example 2
The preparation method of the heterostructure ruthenium cobalt boron-based oxide catalyst in the embodiment comprises the following steps.
1) Preparation of Co-B precursor
1.1 Preparing a cobalt salt solution: 0.9137g of cobalt chloride hexahydrate is weighed and dissolved in deionized water, and the volume is fixed to a 250mL volumetric flask to obtain a cobalt chloride hexahydrate solution with the concentration of 0.015mol/L.
1.2 Preparation of potassium borohydride solution: according to the standard that the molar ratio of cobalt element to boron element is 1:2, 0.4142g of potassium borohydride is weighed, the potassium borohydride is dissolved in deionized water, and the volume is fixed to a 250mL volumetric flask, so that a potassium borohydride solution with the concentration of 0.03mol/L is prepared.
1.3 Preparing a Co-B precursor: slowly dripping 0.03mol/L and 250mL of potassium borohydride solution into 0.015mol/L and 250mL of cobalt chloride hexahydrate solution, stirring continuously, completely reacting after no bubble emerges, standing for half an hour, filtering, and drying in a vacuum drying oven with the vacuum degree of 90Pa and the temperature of 80 ℃ for 10 hours to finally obtain the Co-B precursor.
2) Preparation of Ru-Co-B based oxide catalyst
According to the standard that the molar ratio of ruthenium element to cobalt element is 1:9, weighing 0.0885g of anhydrous ruthenium trichloride; 0.0885g of Co-B precursor is weighed according to the standard of the mass ratio of the Co-B precursor to the anhydrous ruthenium trichloride of 1:1, the precursor and the weighed anhydrous ruthenium trichloride are mixed and fully ground, then the mixed solid particles are put into a low-temperature plasma device, and the Ru-Co-B based oxide catalyst is finally obtained after the power-on treatment for 10min under the voltage of 50V in the air state atmosphere.
The Ru-Co-B-based oxide catalyst prepared in this example was characterized.
1. XRD spectrum
The XRD physical characterization results of the prepared product of this example were the same as those of example 1.
2. Cell performance
Ru-Co-B based oxide prepared in the embodiment is used as anode catalyst of DBFC of borohydride fuel cell, and CeO 2 and/C is cathode catalyst assembly to obtain borohydride fuel cell, and the maximum power density of the fuel cell is measured to reach 165.16mW cm -2 。
Example 3
The preparation method of the heterostructure ruthenium cobalt boron-based oxide catalyst in the embodiment comprises the following steps.
1) Preparation of Co-B precursor
1.1 Preparing a cobalt salt solution: 0.9137g of cobalt chloride hexahydrate is weighed and dissolved in deionized water, and the volume is fixed in a 250mL volumetric flask to obtain a cobalt chloride hexahydrate solution with the concentration of 0.015mol/L;
1.2 Preparation of potassium borohydride solution: according to the standard that the molar ratio of cobalt element to boron element is 1:2, 0.4142g of potassium borohydride is weighed, the potassium borohydride is dissolved in deionized water, and the volume is fixed to a 250mL volumetric flask to prepare a potassium borohydride solution with the concentration of 0.03 mol/L;
1.3 Preparing a Co-B precursor: slowly dripping 0.03mol/L and 250mL of potassium borohydride solution into 0.015mol/L and 250mL of cobalt chloride hexahydrate solution, stirring continuously, completely reacting after no bubble emerges, standing for half an hour, filtering, and drying in a vacuum drying oven with the vacuum degree of 100Pa and the temperature of 100 ℃ for 8 hours to finally obtain a Co-B precursor;
2) Preparation of Ru-Co-B based oxide catalyst
According to the standard that the molar ratio of ruthenium element to cobalt element is 1:10, weighing 0.0798g of anhydrous ruthenium trichloride; 0.0798g of Co-B precursor is weighed according to the standard of the mass ratio of the Co-B precursor to the anhydrous ruthenium trichloride of 1:1, the precursor and the weighed anhydrous ruthenium trichloride are mixed and fully ground, then the mixed solid particles are put into a low-temperature plasma device, and the Ru-Co-B based oxide catalyst is finally obtained after the power-on treatment for 10min under the voltage of 50V in the air state atmosphere.
The Ru-Co-B-based oxide catalyst prepared in this example was characterized.
1. XRD spectrum
The XRD physical characterization results of the prepared product of this example were the same as those of example 1.
2. Cell performance
Ru-Co-B based oxide prepared in the embodiment is used as anode catalyst of DBFC of borohydride fuel cell, and CeO 2 and/C is cathode catalyst assembly to obtain borohydride fuel cell, and the maximum power density of the fuel cell is measured to reach 206.35mW cm -2 。
Example 4
The preparation method of the heterostructure ruthenium cobalt boron catalyst in the embodiment comprises the following steps.
1) Preparation of Co-B precursor
1.1 Preparing a cobalt salt solution: 0.9137g of cobalt chloride hexahydrate is weighed and dissolved in deionized water, and the volume is fixed in a 250mL volumetric flask to obtain a cobalt chloride hexahydrate solution with the concentration of 0.015mol/L;
1.2 Preparation of potassium borohydride solution: according to the standard that the molar ratio of cobalt element to boron element is 1:2, 0.4142g of potassium borohydride is weighed, the potassium borohydride is dissolved in deionized water, and the volume is fixed to a 250mL volumetric flask to prepare a potassium borohydride solution with the concentration of 0.03 mol/L;
1.3 Preparing a Co-B precursor: slowly dripping 0.03mol/L and 250mL of potassium borohydride solution into 0.015mol/L and 250mL of cobalt chloride hexahydrate solution, stirring continuously, completely reacting after no bubble emerges, standing for half an hour, filtering, and drying in a vacuum drying oven with the vacuum degree of 100Pa and 120 ℃ for 6 hours to finally obtain the Co-B precursor.
2) Preparation of Ru-Co-B based oxide catalyst
According to the standard that the molar ratio of ruthenium element to cobalt element is 1:11, weighing 0.0724g of anhydrous ruthenium trichloride; 0.0724g of Co-B precursor is weighed according to the standard of the mass ratio of the Co-B precursor to the anhydrous ruthenium trichloride of 1:1, the precursor and the weighed anhydrous ruthenium trichloride are mixed and fully ground, then the mixed solid particles are put into a low-temperature plasma device, and the Ru-Co-B catalyst is finally obtained after the power-on treatment for 10min under the voltage of 50V in the air state atmosphere.
The Ru-Co-B-based oxide catalyst prepared in this example was characterized.
1. XRD spectrum
The XRD physical characterization results of the prepared product of this example were the same as those of example 1.
2. Cell performance
Ru-Co-B based oxide prepared in the embodiment is used as anode catalyst of DBFC of borohydride fuel cell, and CeO 2 and/C is cathode catalyst assembly to obtain borohydride fuel cell, and the maximum power density of the fuel cell is measured to reach 170.72mW cm -2 。
In conclusion, the Ru-Co-B-based oxide prepared by the method is used as an anode catalyst in the DBFC of the borohydride fuel cell, and the maximum power density of the fuel cell reaches 143.12mW cm -2 ～206.35mW·cm -2 The catalyst has good catalytic activity and better discharge performance.
Further, the performance of the ruthenium cobalt boron-based oxide catalyst prepared by the invention is verified by the following experiment.
Verification 1
Under the same conditions, the ruthenium cobalt boron-based oxide nano-catalyst with the heterostructure prepared in the example 1 is compared with the power of commercial Pt/C, commercial Pt-Ru/C, ruthenium cobalt boron catalyst prepared by a chemical method and cobalt boron catalyst, and the result is shown in FIG. 7.
The ruthenium cobalt boron catalyst prepared by a chemical method comprises the following operation method: the ruthenium salt solution, cobalt salt solution and boride solution prepared in the ratio of example 1 were mixed in sequence at room temperature, and stirred uniformly to obtain a catalyst.
As can be seen from fig. 7, the ruthenium cobalt boron-based oxide nano-catalyst with the heterostructure prepared by using the plasma technology has excellent electrochemical performance, the power of the catalyst is far higher than that of other catalysts, and the discharge performance of the battery is improved. Therefore, the method has good application prospect.
Verification 2
Stability studies were performed on the ruthenium cobalt boron-based oxide catalyst prepared in example 1.
The trend of the change in the battery voltage and discharge time was obtained under constant current discharge for the ruthenium cobalt boron-based oxide catalyst after repeated use for one week, and the result is shown in fig. 8.
Referring to fig. 8, it can be seen that the ruthenium cobalt boron-based oxide catalyst can still have better discharge performance after being used for more than eighty hours under constant current discharge approximately one week, which indicates that the catalyst prepared by the method has good stability and wide commercial application prospect.
The above embodiments are merely a few embodiments of the present invention, and the present invention is not limited thereto, and any simple modification, variation and equivalent changes made to the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the heterostructure ruthenium cobalt boron-based oxide catalyst is characterized by comprising the following steps of:
1) Preparation of Co-B precursor
Respectively weighing cobalt salt and borohydride according to the molar ratio of cobalt element to boron element of 1:2, and obtaining a Co-B precursor through dissolving, stirring, precipitating, separating and drying;
2) Preparation of Ru-Co-B based oxide catalyst
According to the mol ratio of ruthenium element to cobalt element of 1 (4-16), respectively weighing ruthenium salt and Co-B precursor, and carrying out mixed grinding and plasma technology treatment to obtain the Ru-Co-B based oxide catalyst.
2. The method for preparing a heterostructure ruthenium cobalt boron based oxide catalyst according to claim 1, wherein in the step 2), the conditions of the plasma treatment are: the voltage is 40V-70V, the treatment time is 5min-20min, and the temperature is normal temperature.
3. The method for preparing a heterostructure ruthenium cobalt boron based oxide catalyst according to claim 1, wherein in the step 2), the ruthenium salt is anhydrous ruthenium trichloride, ruthenium nitrate, ruthenium sulfate or ruthenium acetate.
4. The method for preparing a heterostructure ruthenium cobalt boron based oxide catalyst according to claim 1, wherein the step 1) specifically comprises the steps of:
1.1 Dissolving the weighed cobalt salt in water to obtain a cobalt salt solution;
1.2 Dissolving the weighed borohydride in water to obtain a borohydride solution;
1.3 Dropwise adding the borohydride solution into the cobalt salt solution, stirring until the reaction is complete, and obtaining the Co-B precursor through standing precipitation, filtering separation and drying.
5. The method for preparing a heterostructure ruthenium cobalt boron based oxide catalyst according to claim 4, wherein in the step 1.1), the concentration of the cobalt salt solution is 0.015mol/L; cobalt salts are cobalt chloride hexahydrate, anhydrous cobalt chloride, cobalt sulfate, cobalt nitrate or cobalt carbonate.
6. The method for preparing a heterostructure ruthenium cobalt boron based oxide catalyst according to claim 4, wherein in the step 1.2), the borohydride is potassium borohydride, sodium borohydride or lithium borohydride, and the concentration of the potassium borohydride solution is 0.03mol/L.
7. The method for preparing a heterostructure ruthenium cobalt boron based oxide catalyst according to claim 4, wherein in the step 1.3), a dropping speed is 1mL/min to 2mL/min; the drying conditions are as follows: vacuum degree is 80Pa-100Pa, temperature is 60 ℃ to 120 ℃ and time is 6h-12h.
8. A ruthenium cobalt boron-based oxide catalyst prepared by the method for preparing a heterostructure ruthenium cobalt boron-based oxide catalyst according to any one of claims 1 to 7, wherein the ruthenium cobalt boron-based oxide catalyst is a core-shell-sheet mosaic heterostructure.
9. Use of a ruthenium cobalt boron-based oxide catalyst according to claim 8 as an anode catalyst in a borohydride fuel cell.
10. The use according to claim 9, wherein the borohydride fuel cell has a maximum power density of 143.12 mW-cm -2 ～206.35mW·cm -2 。
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