CN115050973A - Preparation method of metal oxide modified electrocatalyst for direct formate fuel cell anode - Google Patents
Preparation method of metal oxide modified electrocatalyst for direct formate fuel cell anode Download PDFInfo
- Publication number
- CN115050973A CN115050973A CN202210627138.9A CN202210627138A CN115050973A CN 115050973 A CN115050973 A CN 115050973A CN 202210627138 A CN202210627138 A CN 202210627138A CN 115050973 A CN115050973 A CN 115050973A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- modified
- ultrapure water
- commercial
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 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
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 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
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 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
- 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 17
- 239000007788 liquid Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 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
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- 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
- 238000012805 post-processing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 26
- 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
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000001179 sorption measurement 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
- 150000002505 iron Chemical class 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000012692 Fe precursor Substances 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
- 150000004675 formic acid derivatives Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 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
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 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
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 230000001590 oxidative effect Effects 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant 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
Images
Classifications
-
- 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
-
- 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
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 a commercial palladium-carbon catalyst is treated by an iron salt precursor aqueous solution, generating iron oxide by newly preparing a sodium borohydride aqueous solution; and then carrying out reduced pressure filtration, vacuum drying at 45 ℃, grinding, calcining at 400 ℃ in a tubular furnace for 2h under the argon atmosphere, naturally cooling, and grinding again to obtain the final metal oxide modified commercial palladium-carbon catalyst. Aiming at the characteristic of the electro-catalytic oxidation of formate, the catalyst prepared by the method is more suitable for being directly used for a formate fuel cell anode, 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 a strong adsorption intermediate is effectively promoted, and the activity of the catalyst is improved. Starting from a noble metal catalyst, aiming at the anode reaction characteristics of different types of fuel cells, purposefully modifying and improving the performance.
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 useful in renewable energy conversion devices, can be stored, handled, and transported as a solid or an aqueous solution, has negligible toxicity and high safety, and is an ideal fuel for practical use in fuel cells, as compared to hydrogen, methanol, ethanol, formic acid, and the like.
Currently, the most active catalyst for the electrocatalytic oxidation of formates is a palladium-based metal catalyst. However, the electrooxidation of the formate salt over a pure palladium catalyst presents a reaction intermediate (H) ad ) The problem of too strong adsorption can hinder the adsorption of reactants and influence the reaction. Thus, untreated commercial noble metal catalysts are not ideal catalysts for the electro-oxidation of formate salts and strategies are needed to facilitate the removal of strongly adsorbed intermediates.
To realize high-efficiency electrocatalytic oxidation of formate, the catalyst needs to have the following characteristics: short synthetic route, low cost and high catalytic performance. The commercial palladium-carbon catalyst faces the problem that strongly-adsorbed intermediates are difficult to desorb, and the prepared catalyst enhances the dissociation of water molecules and promotes the adsorption of hydroxyl species (OH) by introducing iron oxide species with oxophilicity ad ) Thereby facilitating the removal of strongly adsorbed intermediates on the palladium sites. Moreover, the commercial noble metal catalyst modification strategy provided by the inventor has the characteristics of short route, low energy consumption, small pollution and strong expansibility, effectively promotes desorption of an intermediate in the process of electrocatalysis of formate oxidation, and improves the activity of the catalyst.
Disclosure of Invention
Aiming at the defect that the existing commercial palladium-carbon catalyst catalyzes formate oxidation, the invention aims to provide a method for conveniently and quickly preparing an electrocatalytic formate oxidation electrocatalyst, which can effectively promote the removal of an intermediate in the reaction process and improve the activity of the intermediate.
In order to solve the technical problem, 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) preparation of commercial catalyst dispersion; weighing a commercial catalyst, carrying out ultrasonic dispersion treatment on the commercial catalyst and ultrapure water together, and carrying out magnetic stirring after the ultrasonic treatment is finished to obtain a dispersion liquid;
(2) configuration of modified precursor liquid; 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, the obtained modified precursor solution is added into a catalyst dispersion liquid to obtain a catalyst mixed liquid;
(4) preparing a precipitating agent; weighing the precipitant, and dissolving in ultrapure water to obtain 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) After drying, carrying out aftertreatment on the crude modified catalyst; grinding the crude modified catalyst in air, then calcining the crude modified catalyst in an inert gas atmosphere, and naturally cooling the crude modified catalyst to room temperature after the calcination is finished. (ii) a
(8) Finally, post-processing; the resulting material was thoroughly ground in air.
The commercial catalyst in the step (1) is selected from palladium carbon, platinum carbon, ruthenium carbon, rhodium carbon, carbon-supported platinum-ruthenium alloy and the like, and the use amounts of the commercial catalyst and ultrapure water are respectively 3-50mL of water for each 20mg of catalyst; the specific treatment time of the ultrasonic treatment is 30 min; and (3) performing magnetic stirring, wherein the specific stirring time is 15min, and a uniform dispersion system is completely formed.
The dosage of the modified precursor and the ultrapure water in the step (2) is respectively 1-20mL of water per 18mg of modified precursor. Wherein the modified precursor is selected from soluble salts of iron, magnesium, aluminum, manganese, cobalt, nickel, copper, zinc, silver and other metals, such as nitrate, chloride, sulfate and the like.
In the 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;
the volume ratio of the ultrapure water for dispersing the commercial catalyst to the ultrapure water for preparing the sodium borohydride solution is less than 50.
And (4) the precipitator in the step (4) is sodium borohydride. The dosages of the sodium borohydride and the ultrapure water are respectively 0.2-100mL of water per 7mg of sodium borohydride.
And (5) 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.
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 the air, the heat treatment temperature is 300-1200 ℃, and the heat treatment time is 1-10 h.
The method has the advantages of simple operation, little pollution and easy realization, and can be used for carrying out targeted modification on the existing catalyst aiming at the characteristic of formate oxidation, and the characteristics are favorable for promoting the practical application of the anode catalyst of the direct formate fuel cell. Based on the existing commercial noble metal catalyst, aiming at the anode reaction characteristics of different types of fuel cells, the corresponding modification is purposefully carried out, and the performance is improved.
Drawings
FIG. 1 shows the electro-catalytic material Pd/FeO for the anode of a direct formate fuel cell according to the present invention x Schematic of the micro-morphology of/C and commercial catalysts;
FIG. 2 shows the electro-catalytic material Pd/FeO for the anode of the direct formate fuel cell according to the present invention x A schematic diagram of X-ray photoelectron spectroscopy of/C;
FIG. 3 is an electrocatalytic process for direct formate fuel cell anodes of the present inventionChemical material Pd/FeO x A schematic diagram of electrochemical performance of/C;
FIG. 4 is a schematic representation of cyclic voltammetry testing of comparative example materials.
FIG. 5 is a graph showing chronoamperometric test results of comparative example materials.
Detailed Description
The following is further detailed by way of specific embodiments: however, the present invention is not limited to the following examples.
Example 1
The preparation method comprises the following steps:
20mg of a commercial palladium-carbon catalyst was weighed, and the catalyst was added to a 50mL beaker together with 6mL of ultrapure water and subjected to ultrasonic dispersion treatment for 30 min. And after the ultrasonic treatment is finished, magnetically stirring for 15min to obtain a dispersion liquid. 18mg of ferric nitrate nonahydrate was weighed and dissolved in 2mL of ultrapure water to obtain an iron precursor solution. Adding the obtained iron precursor solution into the dispersion liquid, and continuously stirring for 30 min. 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 30 min. All products in the beaker are filtered under reduced pressure and washed with ultrapure water for three times. The filter paper with the filter cake is placed in a vacuum drying oven and dried for 12 hours at 45 ℃. The resulting solid was carefully scraped off, placed in an agate mortar and thoroughly ground in air. The powder was spread in a porcelain boat. And (3) placing the porcelain boat containing the powder in a tube furnace, introducing argon for 30min, heating at a speed of 5 ℃/min, and calcining for 2h at 400 ℃ in 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. And obtaining the final catalyst.
In this example, the scanning electron microscope and the transmission electron microscope were used to characterize and analyze the micro-morphology of the electrocatalyst, and it can be seen in fig. 1 that the materials are all supported catalysts supported on carbon carriers.
FIG. 2 shows Pd/FeO as the material of the present invention x An X-ray photoelectron spectrum of/C; it can be seen from figure 2 that the material obtained according to the above process successfully incorporates iron oxide species.
FIG. 3 is a schematic diagram of the electrochemical performance of the material of the present invention; the specific experimental parameters are as follows: setting the scanning range of the cyclic voltammetry potential to be-0.924-0.276V vs. Hg/HgO, and setting the point taking interval to be 0.001V; the sensitivity is 0.001A/V; the electrolyte was a 1M solution of potassium formate and 1M potassium hydroxide, and the test atmosphere was achieved by continuously introducing argon gas into the cell at a flow rate of 30 mL/min. Testing the timing current, setting the potential to be-0.474V vs. Hg/HgO, and taking the point interval to be 0.001V; the sensitivity was 0.001A/V. As can be seen from FIG. 3, the cyclic voltammogram of the material of the invention shows no spikes at-0.18 Vvs. Hg/HgO in the positive sweep at high potential, indicating that the adsorption of intermediates on palladium is inhibited and the mass activity is improved. For palladium on carbon that has not been treated by this method, the peaks indicated by the arrows in the drawing frame correspond to the oxidative desorption of intermediates on palladium at high potential. The strongly adsorbed intermediates are adsorbed on palladium and are difficult to remove at low potential, so that the intermediates can only be oxidized at higher potential, and when scanning is carried out to higher potential, such as the forward scanning process in the figure is carried out to about-0.2V, the curve characteristic that the current acceleration rate is increased greatly appears. The material prepared in the embodiment has no such characteristic, and the cyclic voltammetry characteristic is not observed around-0.2V. The stability of the material is improved by a chronoamperometric test. Therefore, the metal oxide modified commercial palladium carbon electrocatalyst can oxidize and remove the strong adsorption intermediate at low potential, so that the active sites on the palladium are easier to release.
The above description is only an example of the present invention, and the common general knowledge of the known specific structures and characteristics in the schemes is not described too much. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent.
Comparative example 1 (no calcination compared to example 1)
The preparation method comprises the following steps: 20mg of a commercial palladium-carbon catalyst was weighed, and added to a 50mL beaker together with 6mL of ultrapure water, and subjected to ultrasonic dispersion treatment for 30 min. And after the ultrasonic treatment is finished, magnetically stirring for 15min to obtain a dispersion liquid. 18mg of ferric nitrate nonahydrate was weighed and dissolved in 2mL of ultrapure water to obtain an iron precursor solution. Adding the obtained iron precursor solution into the dispersion liquid, and continuously stirring for 30 min. 7mg of sodium borohydride was weighed and dissolved in 2mL of ultrapure water. The sodium borohydride solution was added dropwise to the beaker and magnetic stirring was continued for 30 min. All products in the beaker are filtered under reduced pressure and washed with ultrapure water for three times. The obtained filter paper with the filter cake is placed in a vacuum drying oven and dried for 12 hours at the temperature of 45 ℃. 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 diagram of cyclic voltammetry testing of the comparative example material; the specific experimental parameters are as follows: setting the potential scanning range to be-0.924-0.276V vs. Hg/HgO, and setting the dot extraction interval to be 0.001V; the sensitivity is 0.001A/V; the electrolyte was a 1M solution of potassium formate and 1M potassium hydroxide, and the test atmosphere was achieved by continuously introducing argon gas into the cell at a flow rate of 30 mL/min. As can be seen in fig. 4, the peak corresponding to the desorption of the intermediate occurs again at a high potential after a plurality of cyclic voltammetric scans in the material without heat treatment, and this characteristic shape, which is outlined in the figure, indicates that the material without heat treatment cannot effectively maintain its ability to promote the desorption of the intermediate. In fig. 3, the example material, the cyclic voltammetry positive sweep process, does not observe this feature, indicating that the example material can effectively promote the 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-0.474V vs. Hg/HgO, and the point taking interval is 0.001V; the sensitivity was 0.001A/V. In the comparative example, the magnitude of the current density was lower than that of the original palladium on carbon, and the current decay was very fast, indicating that the material was not heat treated, even less so than the original palladium on carbon.
The above description is only of the 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 important for the synthesis of the material in the present invention.
Claims (10)
1. A preparation method of a metal oxide modified electrocatalyst is characterized by comprising the following steps:
(1) preparation of commercial catalyst dispersion; weighing a commercial catalyst, carrying out ultrasonic dispersion treatment on the commercial catalyst and ultrapure water together, and carrying out magnetic stirring after the ultrasonic treatment is finished to obtain a dispersion liquid;
(2) configuration of modified precursor liquid; 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, the obtained modified precursor solution is added into a catalyst dispersion liquid to obtain a catalyst mixed liquid;
(4) preparing a precipitating agent; weighing the precipitant, and dissolving in ultrapure water to obtain 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) after-treatment of the dried crude modified catalyst; and grinding the crude modified catalyst in the air, calcining the crude modified catalyst in an inert gas atmosphere, and naturally cooling the crude modified catalyst to room temperature after the calcination treatment. (ii) a
(8) Finally, post-processing; the resulting material was thoroughly ground in air.
2. The method according to claim 1, wherein the commercial catalyst in the step (1) is selected from palladium carbon, platinum carbon, ruthenium carbon, rhodium carbon, platinum-on-carbon-ruthenium alloy, etc., and the commercial catalyst and the ultrapure water are used in amounts of 3 to 50mL of water per 20mg of the catalyst, respectively; the specific treatment time of the ultrasonic treatment is 30 min; and (3) performing magnetic stirring, wherein the specific stirring time is 15min, and a uniform dispersion system is completely formed.
3. The method according to claim 1, wherein the modifying precursor and the ultrapure water of the step (2) are used in amounts of 1 to 20mL of water per 18mg of the modifying precursor, respectively; wherein the modified precursor is selected from soluble salts of iron, magnesium, aluminum, manganese, cobalt, nickel, copper, zinc and silver.
4. The method according to claim 1, wherein in the step (3), the mass ratio of the modification precursor to the commercial catalyst is not less than 0.01: 100, not higher than 10: 0.1.
5. The method according to claim 1, wherein the volume ratio of ultrapure water for commercial catalyst dispersion to ultrapure water for preparing the sodium borohydride solution is less than 50.
6. The method of claim 1, wherein the precipitating agent of step (4) is sodium borohydride. The dosages of the sodium borohydride and the ultrapure water are respectively 0.2-100mL of water per 7mg of sodium borohydride.
7. The method according to claim 1, wherein 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 is a method of dropping while performing magnetic stirring of the dispersion.
8. The method according to claim 1, wherein the washing in step (6) with ultrapure water is carried out more than three times, and the drying temperature is 45 ℃; the grinding operation in step (7) should be performed in air, the heat treatment temperature is 300-1200 ℃, and the heat treatment time is 1-10 h.
9. A catalyst prepared by the process of any one of claims 1 to 8.
10. Use of a catalyst prepared according to the process of any one of claims 1 to 8 as an anode for a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210627138.9A CN115050973B (en) | 2022-06-01 | 2022-06-01 | Preparation method of metal oxide modified electrocatalyst for anode of direct formate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210627138.9A CN115050973B (en) | 2022-06-01 | 2022-06-01 | Preparation method of metal oxide modified electrocatalyst for anode of direct formate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115050973A true CN115050973A (en) | 2022-09-13 |
| CN115050973B CN115050973B (en) | 2024-03-26 |
Family
ID=83160452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210627138.9A Active CN115050973B (en) | 2022-06-01 | 2022-06-01 | Preparation method of metal oxide modified electrocatalyst for anode of direct formate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115050973B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110151354A1 (en) * | 2009-12-17 | 2011-06-23 | Samsung Electronics Co., Ltd. | Electrode catalyst for fuel cell, method of manufacturing the same, and fuel cell using the Electrode catalyst |
| 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 |
-
2022
- 2022-06-01 CN CN202210627138.9A patent/CN115050973B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110151354A1 (en) * | 2009-12-17 | 2011-06-23 | Samsung Electronics Co., Ltd. | Electrode catalyst for fuel cell, method of manufacturing the same, and fuel cell using the Electrode catalyst |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115050973B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114293223B (en) | Method for preparing superfine cerium dioxide supported metal monoatomic catalyst from cluster-based framework material | |
| CN112968185B (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN111261886A (en) | Non-noble metal modified platinum-based catalyst for fuel cell and preparation method and application thereof | |
| CN112652780B (en) | Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst | |
| Afzali et al. | Design of PdxIr/g-C3N4 modified FTO to facilitate electricity generation and hydrogen evolution in alkaline media | |
| CN113437314A (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| Gonzalez-Reyna et al. | Nickel supported on carbon nanotubes and carbon nanospheres for ammonia oxidation reaction | |
| CN109731599B (en) | 2D oxygen reduction catalyst Fe3O4Preparation method of @ FeNC nanosheet | |
| CN113659154B (en) | Carbon catalyst for cathode of alkaline fuel cell and preparation method thereof | |
| CN114300693A (en) | Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier | |
| CN114277398A (en) | Preparation method and application of nano-copper catalyst | |
| CN113889632A (en) | Preparation method of N-doped hollow mesoporous carbon shell-supported PtNi alloy octahedral catalyst | |
| CN109908887B (en) | Nano metal bismuth catalyst supported by micro-oxidation conductive carbon black and application thereof | |
| CN116544429A (en) | Preparation method and application of MnO/Mn-N-C catalyst | |
| CN111129525A (en) | Carbon carrier for fuel cell, preparation method thereof and application thereof in fuel cell | |
| CN115050973B (en) | Preparation method of metal oxide modified electrocatalyst for anode of direct formate fuel cell | |
| CN114672846B (en) | For electrocatalytic CO 2 Preparation and application of reduced bimetallic catalytic material | |
| CN113684499B (en) | Preparation method and application of nickel-nitrogen co-doped carbon-based catalyst with high metal loading efficiency | |
| CN114807981A (en) | High-efficiency synthesis of H 2 O 2 Preparation method and application of Zn-N-C electrocatalyst | |
| CN113903934A (en) | Preparation method and application of porous Pd-PdO nanorod | |
| CN112002916A (en) | Transition metal doped anode catalyst and preparation method and application thereof | |
| CN113629262A (en) | Proton exchange membrane fuel cell cathode catalyst based on high-activity carbon fiber material | |
| CN113549948B (en) | Surface amino modified Cu @ NH 2 Nano catalyst, preparation method and application thereof | |
| CN114717597B (en) | Molecular cage coated metal core-shell material and preparation method and application thereof | |
| CN115020719A (en) | Preparation method of dual-site catalyst for direct formate fuel cell anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |