CN115050973B - Preparation method of metal oxide modified electrocatalyst for anode of direct formate fuel cell - Google Patents
Preparation method of metal oxide modified electrocatalyst for anode of direct formate fuel cell Download PDFInfo
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- CN115050973B CN115050973B CN202210627138.9A CN202210627138A CN115050973B CN 115050973 B CN115050973 B CN 115050973B CN 202210627138 A CN202210627138 A CN 202210627138A CN 115050973 B CN115050973 B CN 115050973B
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- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title claims abstract description 21
- 239000000446 fuel Substances 0.000 title claims abstract description 18
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 26
- 239000012498 ultrapure water Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Chemical class 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 claims description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- -1 silver metals Chemical class 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052763 palladium Inorganic materials 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000012300 argon atmosphere Substances 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000012692 Fe precursor Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 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
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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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
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
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Abstract
A preparation method of a metal oxide modified electrocatalyst for a direct formate fuel cell anode belongs to the field of fuel cell anode catalysts. After the commercial palladium-carbon catalyst is treated by ferric salt precursor aqueous solution, the generation of iron oxide is realized by newly preparing sodium borohydride aqueous solution; and then carrying out reduced pressure filtration, vacuum drying at 45 ℃, grinding, calcining at 400 ℃ in a tube furnace for 2 hours under the argon atmosphere, and then naturally cooling and grinding again to obtain the final metal oxide modified commercial palladium-carbon catalyst. Aiming at the characteristics of electrocatalytic oxidation of formate, the catalyst prepared by the method is more suitable for anodes of direct formate fuel cells, and the introduced metal oxide particles are dispersed around the original palladium metal particles of the commercial noble metal catalyst, so that the desorption of the strong adsorption intermediate is effectively promoted and the activity of the catalyst is improved. Starting from noble metal catalyst, the anode reaction characteristics of different types of fuel cells are purposefully modified, so that the performance is improved.
Description
Technical Field
The invention belongs to the field of fuel cell anode catalysts, and particularly discloses a preparation method of a metal oxide modified electrocatalyst for a direct formate fuel cell anode.
Technical Field
Formate as a compound which can be used in renewable energy conversion devices, compared with hydrogen, methanol, ethanol, formic acid, etc., can be stored, handled and transported in the form of solid or aqueous solution, has negligible toxicity and high safety, and is ideal fuel for practical use in fuel cells.
Currently, the catalyst with the highest electrocatalytic oxidation activity for formate is a palladium-based metal catalyst. However, in the electrooxidation of formate on pure palladium catalyst, a reaction intermediate (H ad ) The problem of too strong adsorption can hinder the adsorption of reactants and affect the reaction. Thus, untreated commercial noble metal catalysts are not ideal catalysts for catalyzing formate electrooxidation, and some strategies are required to facilitate removal of strongly adsorbed intermediates.
The catalyst used for realizing high-efficiency electrocatalytic formate oxidation needs to have the following characteristics: short synthetic route, low cost and high catalytic performance. Commercial palladium-carbon catalysts suffer from the problem that strong adsorption intermediates are difficult to desorb, and the prepared catalyst enhances the dissociation of water molecules by introducing an iron oxide species with oxygen affinity, thereby promoting the adsorption of hydroxyl species (OH ad ) Thereby facilitating the removal of strongly adsorbed intermediates at the palladium sites. Moreover, the commercial noble metal catalyst modification strategy provided by the method has the characteristics of short route, low energy consumption, small pollution and strong expansibility, and effectively promotes the desorption of intermediates in the process of electrocatalytic formate oxidation, and the catalyst activity is also improved.
Disclosure of Invention
Aiming at the defect of formate oxidation catalyzed by the prior commercial palladium-carbon catalyst, the invention aims to provide a method for conveniently and rapidly preparing an electrocatalytic formate oxidation electrocatalyst, which can effectively promote the removal of intermediates in the reaction process and improve the activity of the intermediates.
In order to solve the technical problems, the invention provides a preparation method of a metal oxide modified electrocatalyst for a direct formate fuel cell anode, which comprises the following steps:
(1) The preparation of commercial catalyst dispersions; weighing a commercial catalyst, carrying out ultrasonic dispersion treatment on the commercial catalyst and ultrapure water, and magnetically stirring after ultrasonic treatment is finished to obtain a dispersion liquid;
(2) Preparing a modified precursor liquid; and weighing the modified precursor, and dissolving the modified precursor in ultrapure water to obtain a modified precursor solution.
(3) Mixing the catalyst dispersion liquid in the step (1) and the modified precursor solution in the step (2); preferably, adding the obtained modified precursor solution into a catalyst dispersion liquid to obtain a catalyst mixed liquid;
(4) Preparing a precipitant; weighing the precipitant, and dissolving the precipitant in ultrapure water to obtain a precipitant solution.
(5) Preparing a crude modified catalyst; mixing the precipitant solution of the step (4) with the catalyst of the step (3);
(6) Purifying the crude modified catalyst; filtering under reduced pressure, washing, and vacuum drying.
(7) Post-treatment of the crude modified catalyst after drying; grinding the crude modified catalyst in air, calcining in inert gas atmosphere, and naturally cooling to room temperature. The method comprises the steps of carrying out a first treatment on the surface of the
(8) Final post-treatment; the resulting material was thoroughly ground in air.
The commercial catalyst is selected from palladium carbon, platinum carbon, ruthenium carbon, rhodium carbon, carbon-supported platinum-ruthenium alloy and the like, and the dosage of the commercial catalyst and the ultrapure water is respectively 3-50mL of water corresponding to each 20mg of catalyst; the specific treatment time of the ultrasonic treatment is 30min; the magnetic stirring is carried out for 15min, and a uniform dispersion system is completely formed.
The dosage of the modified precursor and the ultrapure water in the step (2) is 1-20mL of water for each 18mg of modified precursor. Wherein the modified precursor is selected from soluble salts of metals such as iron, magnesium, aluminum, manganese, cobalt, nickel, copper, zinc, silver, etc., such as nitrate, chloride, sulfate, etc.
In step (3), the mass ratio of the modified precursor to the commercial catalyst should be not less than 0.01:100, not higher than 10:0.1;
the volume ratio of the commercial catalyst dispersion ultrapure water to the ultrapure water used to prepare the sodium borohydride solution should be less than 50.
The precipitant in the step (4) is sodium borohydride. The dosage of the sodium borohydride and the ultrapure water is respectively 0.2-100mL of water for every 7mg of sodium borohydride.
The mass ratio of the sodium borohydride to the modified precursor in the step (5) is more than 0.25, and the two-solution mixing method adopts a mode of dropwise adding while magnetically stirring the dispersion liquid.
And (6) washing with ultrapure water for more than three times, wherein the drying temperature is 45 ℃.
The grinding operation in the step (7) is carried out in air, the heat treatment temperature is 300-1200 ℃, and the heat treatment time is 1-10h.
The method is simple to operate, has little pollution and is easy to realize, the existing catalyst is pertinently modified according to formate oxidation characteristics, and the characteristics are beneficial to promoting the practical application of the anode catalyst of the direct formate fuel cell. Starting from the existing commercial noble metal catalyst, aiming at the anode reaction characteristics of different types of fuel cells, corresponding modification is purposefully carried out, and the performance is improved.
Drawings
FIG. 1 shows the electrocatalytic material Pd/FeO for direct formate fuel cell anode of the present invention x Schematic of the microscopic morphology of the/C and commercial catalysts;
FIG. 2 shows the electrocatalytic material Pd/FeO for direct formate fuel cell anode of the present invention x An X-ray photoelectron spectroscopy schematic of/C;
FIG. 3 shows the electrocatalytic material Pd/FeO for direct formate fuel cell anode of the present invention x Schematic of the electrochemical performance of/C;
FIG. 4 is a schematic representation of cyclic voltammetry testing of a comparative example material.
FIG. 5 is a graph showing the results of the comparative example material chronoamperometric test.
Detailed Description
The following is a further detailed description of the embodiments: the present invention is not limited to the following examples.
Example 1
The preparation method comprises the following steps:
20mg of a commercial palladium on charcoal catalyst was weighed, added to a 50mL beaker together with 6mL of ultrapure water, and sonicated for 30min. After the ultrasonic treatment, magnetically stirring for 15min to obtain dispersion. 18mg of ferric nitrate nonahydrate was weighed and dissolved in 2mL of ultrapure water to obtain an iron precursor solution. The obtained iron precursor solution was added to the dispersion, and stirring was continued for 30min. 7mg of sodium borohydride was weighed out and dissolved in 2mL of ultrapure water. The sodium borohydride solution was added dropwise to the beaker and magnetic stirring was continued for 30min. All the products in the beaker were filtered under reduced pressure and washed three times with ultrapure water. The filter paper with the filter cake obtained was placed in a vacuum drying oven and dried at 45℃for 12 hours. The resulting solid was carefully scraped off, placed in an agate mortar, and thoroughly ground in air. The powder is spread in a porcelain boat. Placing the porcelain boat containing the powder into a tube furnace, introducing argon for 30min, heating at a rate of 5 ℃/min, and calcining at 400 ℃ for 2h under an argon atmosphere. And naturally cooling to room temperature after the calcination is finished. The resulting powder was placed in an agate mortar and thoroughly ground in air. Obtaining the final catalyst.
In this embodiment, the microscopic morphology of the electrocatalyst was characterized and analyzed by using a scanning electron microscope and a transmission electron microscope, and it can be seen in fig. 1 that the materials are supported catalysts supported on a carbon carrier.
FIG. 2 is a Pd/FeO material of the present invention x X-ray photoelectron spectrum of/C; it can be seen from fig. 2 that the material obtained according to the above method successfully incorporates iron oxide species.
FIG. 3 is a schematic representation of the electrochemical performance of the material of the present invention; the specific experimental parameters are as follows: the cyclic voltammetry potential scanning range is set to be-0.924-0.276V vs. Hg/HgO, and the sampling interval is 0.001V; sensitivity was 0.001A/V; the electrolyte was 1M potassium formate and 1M potassium hydroxide solution, and the test atmosphere was continuously vented into the cell at an argon gas flow rate of 30 mL/min. Timing current test, wherein the potential is set to be-0.474V vs. Hg/HgO, and the sampling interval is 0.001V; the sensitivity was 0.001A/V. As can be seen from FIG. 3, in the cyclic voltammogram of the material of the invention, no peak appears in the figure at the time of minus 0.18Vvs. Hg/HgO under the positive sweep range and high potential, which indicates that the adsorption of an intermediate on palladium is inhibited and the quality activity is improved. Whereas for palladium on carbon not treated by the present method, the peak indicated by the arrow in the frame of the figure corresponds to the oxidative desorption of the palladium intermediate at high potential. The strong adsorption intermediate is adsorbed on palladium and is difficult to remove under low potential, so that the strong adsorption intermediate can only be oxidized under higher potential, and therefore when the scanning is carried out to higher potential, as the forward scanning process in the figure is carried out to about-0.2V, curve characteristics of current acceleration and enlargement can appear. The material prepared in this example, however, did not have this feature and no cyclic voltammetry was observed around-0.2V. The stability of the invented material is also improved by the time-current test. It follows that metal oxide modification of commercial palladium on carbon electrocatalysts allows the oxidative removal of strongly adsorbed intermediates at low potentials, thus releasing the active sites on palladium more easily.
The foregoing is merely exemplary embodiments of the present invention, and specific structures and features that are well known in the art are not described in detail. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent.
Comparative example 1 (with respect to example 1 without calcination)
The preparation method comprises the following steps: 20mg of a commercial palladium on charcoal catalyst was weighed, added to a 50mL beaker together with 6mL of ultrapure water, and sonicated for 30min. After the ultrasonic treatment, magnetically stirring for 15min to obtain dispersion. 18mg of ferric nitrate nonahydrate was weighed and dissolved in 2mL of ultrapure water to obtain an iron precursor solution. The obtained iron precursor solution was added to the dispersion, and stirring was continued for 30min. 7mg of sodium borohydride was weighed out and dissolved in 2mL of ultrapure water. The sodium borohydride solution was added dropwise to the beaker and magnetic stirring was continued for 30min. All the products in the beaker were filtered under reduced pressure and washed three times with ultrapure water. The filter paper with the filter cake obtained was placed in a vacuum drying oven and dried at 45℃for 12 hours. The resulting solid was carefully scraped off, placed in an agate mortar, and thoroughly ground in air.
In this comparative example, electrochemical performance of the electrocatalyst was evaluated using chronoamperometry and cyclic voltammetry.
FIG. 4 is a schematic illustration of cyclic voltammetry testing of the material of this comparative example; the specific experimental parameters are as follows: the potential scanning range is set to be-0.924-0.276V vs. Hg/HgO, and the sampling interval is 0.001V; sensitivity was 0.001A/V; the electrolyte was 1M potassium formate and 1M potassium hydroxide solution, and the test atmosphere was continuously vented into the cell at an argon gas flow rate of 30 mL/min. As can be seen from fig. 4, after a plurality of cyclic voltammetric scans, the material without heat treatment, which corresponds to the peak of desorption of the intermediate, appears again at a high potential, and this characteristic shape is outlined in the figure, indicating that the material without heat treatment cannot effectively maintain its ability to promote desorption of the intermediate. In fig. 3, this feature is not observed for the example material during cyclic voltammetry, indicating that the example material is effective in facilitating intermediate removal.
Fig. 5 is a schematic diagram of the timing current test result of the comparative example material, and the specific experimental parameters are as follows: the potential is set to be-0.474V vs. Hg/HgO, and the point taking interval is 0.001V; the sensitivity was 0.001A/V. In the comparative example, the current density was lower than that of the original palladium on charcoal, and the current decayed rapidly, indicating that the material without heat treatment was even inferior to the original palladium on charcoal.
The above description is merely a comparative example of the present invention, and is sufficient to illustrate the importance of step (8) in the present invention, and the heat treatment parameters are critical to the synthesis of the materials in the present invention.
Claims (9)
1. A method for preparing a metal oxide modified electrocatalyst for a formate fuel cell anode, comprising the steps of:
(1) The preparation of commercial catalyst dispersions; weighing a commercial catalyst, carrying out ultrasonic dispersion treatment on the commercial catalyst and ultrapure water, and magnetically stirring after ultrasonic treatment is finished to obtain a dispersion liquid;
(2) Preparing a modified precursor liquid; weighing a modified precursor, and dissolving the modified precursor in ultrapure water to obtain a modified precursor solution;
(3) Mixing the catalyst dispersion liquid in the step (1) and the modified precursor solution in the step (2);
(4) Preparing a precipitant; weighing a precipitant, and dissolving the precipitant in ultrapure water to obtain a precipitant solution;
(5) Preparing a crude modified catalyst; mixing the precipitant solution of the step (4) with the catalyst of the step (3);
(6) Purifying the crude modified catalyst; filtering under reduced pressure, washing, and vacuum drying;
(7) Post-treatment of the crude modified catalyst after drying; grinding the crude modified catalyst in air, calcining the crude modified catalyst in an inert gas atmosphere, and naturally cooling the crude modified catalyst to room temperature after the calcination;
(8) Final post-treatment; fully grinding the obtained material in air;
the commercial catalyst in the step (1) is selected from one of palladium carbon, platinum carbon, ruthenium carbon, rhodium carbon and platinum-ruthenium alloy carried by carbon, and the use amount of the commercial catalyst and the ultrapure water is 3-50mL water corresponding to each 20mg catalyst;
the dosage of the modified precursor and the ultrapure water in the step (2) is 1-20mL water for each 18mg modified precursor; wherein the modified precursor is selected from one or more of soluble salts of iron, magnesium, aluminum, manganese, cobalt, nickel, copper, zinc and silver metals; the precipitant in the step (4) is sodium borohydride; the dosage of the sodium borohydride and the ultrapure water is respectively 0.2-100mL water for every 7mg sodium borohydride.
2. The method according to claim 1, wherein the ultrasonic dispersion treatment is performed for a specific treatment time of 30 minutes; the magnetic stirring is carried out for 15min, and a uniform dispersion system is completely formed.
3. The method according to claim 1, wherein the step (3) is to add the obtained modified precursor solution to a catalyst dispersion to obtain a catalyst mixture.
4. The method of claim 1, wherein in step (3), the mass ratio of the modified precursor to the commercial catalyst is not less than 0.01:100, not higher than 10:0.1.
5. The method of claim 1, wherein the volume ratio of ultrapure water used for commercial catalyst dispersion to ultrapure water used for preparing the sodium borohydride solution is less than 50.
6. The method according to claim 1, wherein the mass ratio of sodium borohydride to the modified precursor in the step (5) is greater than 0.25, and the two-solution mixing method is a method of dropwise adding the dispersion liquid while magnetically stirring the dispersion liquid.
7. The method of claim 1, wherein step (6) is performed with more than three times of washing with ultrapure water at a drying temperature of 45 ℃; the grinding operation in the step (7) is carried out in air, the calcination treatment temperature is 300-1200 ℃, and the calcination treatment time is 1-10h.
8. A catalyst prepared according to the method of any one of claims 1-7.
9. Use of a catalyst prepared according to the method of any one of claims 1-7 as a fuel cell anode.
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| CN105576263A (en) * | 2015-12-16 | 2016-05-11 | 中国科学院等离子体物理研究所 | High-performance fuel cell catalyst and preparation method thereof |
| CN106935872A (en) * | 2017-03-07 | 2017-07-07 | 福州大学 | A kind of preparation method of the modified fuel battery anode catalyst of precipitating reagent |
| CN108630956A (en) * | 2018-04-26 | 2018-10-09 | 哈尔滨师范大学 | A kind of direct methanoic acid fuel cell palladium-based catalyst carrier and preparation method thereof |
| CN109713325A (en) * | 2018-12-29 | 2019-05-03 | 四川大学 | A kind of preparation method of palladium nano catalyst used for direct methanoic acid fuel cell |
| CN113594483A (en) * | 2021-07-28 | 2021-11-02 | 宁波中科科创新能源科技有限公司 | Preparation method of PtCo intermetallic compound catalyst and fuel cell |
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| KR101572123B1 (en) * | 2009-12-17 | 2015-11-26 | 삼성전자주식회사 | Electrode catalyst for fuel cell manufacturing method thereof and fuel cell using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105576263A (en) * | 2015-12-16 | 2016-05-11 | 中国科学院等离子体物理研究所 | High-performance fuel cell catalyst and preparation method thereof |
| CN106935872A (en) * | 2017-03-07 | 2017-07-07 | 福州大学 | A kind of preparation method of the modified fuel battery anode catalyst of precipitating reagent |
| CN108630956A (en) * | 2018-04-26 | 2018-10-09 | 哈尔滨师范大学 | A kind of direct methanoic acid fuel cell palladium-based catalyst carrier and preparation method thereof |
| CN109713325A (en) * | 2018-12-29 | 2019-05-03 | 四川大学 | A kind of preparation method of palladium nano catalyst used for direct methanoic acid fuel cell |
| CN113594483A (en) * | 2021-07-28 | 2021-11-02 | 宁波中科科创新能源科技有限公司 | Preparation method of PtCo intermetallic compound catalyst and fuel cell |
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