CN114171745A - Method for optimizing carbon-supported platinum-based alloy catalyst process - Google Patents
Method for optimizing carbon-supported platinum-based alloy catalyst process Download PDFInfo
- Publication number
- CN114171745A CN114171745A CN202111178260.4A CN202111178260A CN114171745A CN 114171745 A CN114171745 A CN 114171745A CN 202111178260 A CN202111178260 A CN 202111178260A CN 114171745 A CN114171745 A CN 114171745A
- Authority
- CN
- China
- Prior art keywords
- platinum
- carbon
- based alloy
- supported platinum
- compound
- 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.)
- Pending
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 34
- 239000000956 alloy Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 229910052723 transition metal Inorganic materials 0.000 claims description 15
- 150000003624 transition metals Chemical class 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000005457 optimization Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal formate Chemical class 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000011268 mixed slurry Substances 0.000 description 12
- 229910000990 Ni alloy Inorganic materials 0.000 description 10
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- UBZYWIKLAYTIOV-UHFFFAOYSA-N [Na].CC=O Chemical compound [Na].CC=O UBZYWIKLAYTIOV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000013386 optimize process Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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
-
- 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
The invention provides a method for optimizing a carbon-supported platinum-based alloy catalyst process, which comprises the steps of dissolving a platinum-containing precursor compound, a complexing agent and an auxiliary inorganic salt compound in water to form a solution, keeping the pH value of the solution at 3-8, and standing for 24-72 hours at 10-40 ℃ to obtain a mixed solution; adding a reducing agent compound and carbon-supported platinum-based alloy powder into the mixed solution, reacting at 20-50 ℃ for 30-180 minutes, and filtering and drying the reaction product to obtain the carbon-supported platinum-based alloy catalyst. The method has simple and feasible process, and the prepared carbon-supported platinum-based alloy catalyst has the advantages of high catalyst active component loading, complete platinum covering of the active component outer layer, high catalyst stability and the like.
Description
Technical Field
The invention relates to a preparation method of a supported metalloid catalyst, in particular to a method for optimizing a carbon-supported platinum-based alloy catalyst process.
Background
At present, catalysts for proton exchange membrane fuel cells are carbon-supported metal platinum catalysts, and in order to reduce the use amount of noble metal platinum, various carbon-supported alloy catalysts formed by platinum and transition metals such as nickel, cobalt, iron and the like are proposed, for example, patent application 2020105709768 discloses a preparation method of the catalysts, and the alloy catalysts suitable for proton exchange membrane fuel cells are prepared. However, due to the large difference between the reduction potentials of the transition metal and the noble metal platinum and the difference between the reduction reaction speeds, the materials formed after the reduction reaction contain transition metals or oxides of the transition metals which do not form an alloy with the platinum, and the metals or the oxides do not have catalytic activity, and the inactive components are usually removed by acid washing in the existing preparation process, but after the inactive components are removed by acid washing, the carbon carrier is exposed, or the surface part of the alloy is hollowed out, so that the quality activity and the stability of the catalyst are influenced.
Disclosure of Invention
The invention aims to provide an optimization method of a preparation process of a carbon-supported platinum-based alloy catalyst, so as to reduce or even remove 'hollow-out' on the surface of a catalyst alloy, reduce the exposure condition of a carbon carrier and improve the quality activity and stability of the catalyst. The invention is realized by the following scheme:
a method for optimizing a carbon-supported platinum-based alloy catalyst process comprises the following steps:
dissolving a platinum-containing precursor compound, a complexing agent and an auxiliary inorganic salt compound in water to form a solution, keeping the pH value of the solution at 3-8, and standing at 10-40 ℃ for 24-72 hours to obtain a mixed solution; the platinum-containing precursor compound is selected from one or more of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, potassium chloroplatinate or sodium chloroplatinate, the complexing agent is selected from one or more of formaldehyde, acetaldehyde, citric acid and sodium citrate, and the auxiliary inorganic salt compound is selected from one or more of nitric acid of alkali metal and halide of alkali metal;
(II) adding a reducing agent compound and a carbon-loaded platinum-based alloy powder material into the mixed solution prepared in the step I, reacting for 30-180 minutes at 20-50 ℃, and filtering and drying; the carbon-supported platinum-based alloy powder material is an alloy formed by carbon-supported platinum and transition metal, and the transition metal is selected from one or more of nickel, cobalt, iron or copper; the reducing agent compound is selected from one or more of ascorbic acid, formic acid, acetic acid, alkali metal formate, alkali metal acetate, acetaldehyde and alkali metal acetaldehyde compound.
In the step II, the molar ratio of platinum in the mixed solution prepared in the step I to transition metal in the carbon-supported platinum-based alloy powder material is 1 (5-10); the molar ratio of the platinum to the reducing agent compound in the mixed solution is 1 (2-10), so that the filling effect is better, and the catalyst performance is better.
The carbon-supported platinum-based alloy powder material in the above step can be prepared by the scheme as in patent application 2020105709768.
The method for optimizing the process of preparing the carbon-supported platinum-based alloy catalyst comprises the steps of carrying out further treatment on the material by utilizing the reduction reaction of platinum after the existing carbon-supported platinum-based alloy catalyst process, filling the bare dew point of a carbon carrier and the hollow-out point of the surface part of the alloy which are formed by transition metal or oxide of the transition metal which does not form alloying with the platinum by utilizing a small amount of platinum, completely covering the outer layer of the active component by the platinum, improving the loading capacity of the active component of the catalyst and simultaneously improving the stability of the catalyst. And the optimization process is simple and feasible and has low energy consumption.
Drawings
FIG. 1 is a transmission electron microscope image of a carbon-supported platinum-based alloy catalyst prepared by the optimized process of example 1
FIG. 2 Transmission Electron microscopy of carbon-loaded platinum-based alloy catalyst without optimization of the Process
Detailed Description
The invention will be further described with reference to the following examples and drawings, but the invention is not limited to the examples.
Example 1
The method disclosed in patent application 2020105709768 is used to prepare a carbon-supported platinum-nickel alloy catalyst, and comprises the following steps: adding activated carbon into an aqueous solution of chloroplatinic acid and nickel chloride, and uniformly mixing to obtain mixed slurry, wherein the mass of platinum in the chloroplatinic acid is 40% of that of the activated carbon, and the molar ratio of the chloroplatinic acid to the nickel chloride is 3: 1, placing the mixed slurry in an ice bath to be cooled to 0 ℃, rapidly adjusting the pH value of the mixed slurry to 12-14 within 2 minutes by using a strong base solution, then rapidly freezing the mixed slurry in liquid nitrogen within 1 minute, drying, placing the product after freeze drying in a hydrogen-nitrogen volume ratio of 5: and (3) carrying out heat treatment for 6h in a reducing atmosphere formed by 95 mixed gas at the temperature of 700 ℃, and then filtering, pickling, washing with water and drying to obtain the carbon-supported platinum-nickel alloy catalyst powder.
The carbon-supported platinum-nickel alloy catalyst powder material is optimized according to the following steps:
dissolving chloroplatinic acid, sodium citrate and sodium nitrate in water to form a solution, wherein the molar ratio of platinum to sodium citrate in the chloroplatinic acid is 1:10, the mole ratio of platinum to sodium nitrate in chloroplatinic acid is 1:5, adjusting and keeping the pH value of the solution to be 3-5 by using sodium hydroxide, and standing for 72 hours at 10 ℃ to obtain a mixed solution;
(II) adding 0.001mol/L ascorbic acid and carbon-supported platinum-nickel alloy catalyst powder into the mixed solution obtained in the step I, wherein the mixing amount of the substances is determined according to the following ratio: the molar ratio of platinum in the mixed solution to the transition metal nickel in the carbon-supported platinum-based alloy powder material is 1:10, the molar ratio of platinum in the mixed solution to ascorbic acid is 1:10, the reaction is carried out for 180 minutes at 20 ℃, and the optimized carbon-supported platinum-nickel alloy catalyst is prepared by filtering and drying the product after the reaction.
The carbon-supported platinum-nickel alloy catalyst subjected to the optimization and the carbon-supported platinum-nickel alloy catalyst powder not subjected to the optimization process are respectively observed on a transmission electron microscope, and the results are respectively shown in fig. 1 and 2. From the figure, it can be found that the platinum-nickel alloy catalyst after being optimized has greatly reduced exposed area and obviously increased loading amount of active components (dark dots in the figure). The charge and discharge performance of the two catalysts are respectively tested under the same condition, and the result shows that the platinum-nickel alloy catalyst treated by the optimized process can improve the mass activity from 0.47A/mg @0.9V to 0.65A/mg @ 0.9V; after 3 ten thousand times of cycle tests at 0.6-0.95V, the mass activity loss can be improved from less than 40% before optimization to less than 30%, and the stability is obviously improved.
Example 2
The method disclosed in patent application 2020105709768 is used to prepare a carbon-supported platinum-cobalt alloy catalyst, and comprises the following steps: adding carbon fibers into an aqueous solution of sodium chloroplatinite and cobalt acetate, and uniformly mixing to obtain mixed slurry, wherein the mass of platinum in the sodium chloroplatinite is 40% of that of the carbon fibers, and the molar ratio of the sodium chloroplatinite to the cobalt acetate is 1:1, placing the mixed slurry in an ice bath to cool to-2 ℃, rapidly adjusting the pH value of the mixed slurry to 12-14 within 2 minutes by using a potassium hydroxide strong base solution, then rapidly freezing the mixed slurry by using liquid nitrogen within 30 seconds, drying, placing the product after freeze drying in a hydrogen-nitrogen gas volume ratio of 5: and (3) carrying out heat treatment for 9h in a reducing atmosphere formed by 95 mixed gas at the temperature of 550 ℃, and then filtering, pickling, washing with water and drying to obtain the carbon-loaded platinum-cobalt alloy catalyst powder.
The carbon-supported platinum-cobalt alloy catalyst powder material is optimized according to the following steps:
dissolving sodium chloroplatinite, acetaldehyde and potassium chloride in water to form a solution, wherein the molar ratio of platinum to acetaldehyde in the sodium chloroplatinite is 1:1, the mole ratio of platinum to sodium nitrate in chloroplatinic acid is 1: 15, adjusting and maintaining the pH value of the solution to be 4-8 by using sodium hydroxide, and standing for 24 hours at 40 ℃ to obtain a mixed solution;
(II) adding 0.05mol/L of sodium formate and carbon-supported platinum-cobalt alloy catalyst powder into the mixed solution obtained in the step I, wherein the mixing amount of the substances is determined according to the following proportion: the molar ratio of platinum in the mixed solution to the transition metal cobalt in the carbon-supported platinum-based alloy powder material is 1:5, the molar ratio of platinum in the mixed solution to sodium formate is 1:4, the reaction is carried out for 30 minutes at 50 ℃, and the optimized carbon-supported platinum-nickel alloy catalyst is prepared by filtering and drying the product after the reaction.
Example 3
The method disclosed in patent application 2020105709768 is used to prepare a carbon-supported platinum-copper alloy catalyst, and comprises the following steps: adding graphene into an aqueous solution of chloroplatinic acid and copper sulfate, and uniformly mixing to obtain a mixed slurry, wherein the mass of platinum in the chloroplatinic acid is 40% of that of the graphene, and the molar ratio of the chloroplatinic acid to the copper sulfate is 4: 1, placing the mixed slurry in an ice bath to be cooled to 1 ℃, rapidly adjusting the pH value of the mixed slurry to 12-14 within 5 minutes by using a potassium hydroxide strong base solution, then rapidly freezing the mixed slurry by using liquid nitrogen within 2 minutes, drying, placing the frozen and dried product in a hydrogen atmosphere and carrying out heat treatment for 8 hours at the temperature of 700 ℃, and then filtering, acid washing, water washing and drying to obtain the carbon-loaded platinum-copper alloy catalyst powder.
The carbon-supported platinum-copper alloy catalyst powder material is optimized according to the following steps:
dissolving chloroplatinic acid, citric acid and potassium nitrate in water to form a solution, wherein the molar ratio of platinum to citric acid in the chloroplatinic acid is 1: 20, the mole ratio of platinum to potassium nitrate in chloroplatinic acid is 1: 30, regulating and maintaining the pH value of the solution to be 3-7 by using potassium hydroxide, and standing for 50 hours at the temperature of 30 ℃ to obtain a mixed solution;
(II) adding 0.005mol/L sodium acetaldehyde and carbon-supported platinum-copper alloy catalyst powder into the mixed solution obtained in the step I, wherein the mixing amount of the substances is determined according to the following ratio: the molar ratio of platinum in the mixed solution to transition metal copper in the carbon-supported platinum-based alloy powder material is 1:7, the molar ratio of platinum in the mixed solution to acetaldehyde sodium is 1:2, the reaction is carried out for 90 minutes at the temperature of 40 ℃, and the optimized carbon-supported platinum-copper alloy catalyst is prepared by filtering and drying the product after the reaction.
Claims (3)
1. A method for optimizing a carbon-supported platinum-based alloy catalyst process is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
dissolving a platinum-containing precursor compound, a complexing agent and an auxiliary inorganic salt compound in water to form a solution, keeping the pH value of the solution at 3-8, and standing at 10-40 ℃ for 24-72 hours to obtain a mixed solution; the platinum-containing precursor compound is selected from one or more of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, potassium chloroplatinate or sodium chloroplatinate, the complexing agent is selected from one or more of formaldehyde, acetaldehyde, citric acid and sodium citrate, and the auxiliary inorganic salt compound is selected from one or more of nitric acid of alkali metal and halide of alkali metal;
(II) adding a reducing agent compound and a carbon-loaded platinum-based alloy powder material into the mixed solution prepared in the step I, reacting for 30-180 minutes at 20-50 ℃, and filtering and drying; the carbon-supported platinum-based alloy powder material is an alloy formed by carbon-supported platinum and transition metal, and the transition metal is selected from one or more of nickel, cobalt, iron or copper; the reducing agent compound is selected from one or more of ascorbic acid, formic acid, acetic acid, alkali metal formate, alkali metal acetate, acetaldehyde and alkali metal acetaldehyde compound.
2. The method for process optimization of a carbon-supported platinum-based alloy catalyst according to claim 1, wherein: in the step II, the molar ratio of platinum in the mixed solution prepared in the step I to transition metal in the carbon-supported platinum-based alloy powder material is 1 (5-10).
3. The method for process optimization of a carbon-supported platinum-based alloy catalyst according to claim 1 or 2, wherein: in the step II, the molar ratio of the platinum in the mixed solution prepared in the step I to the reducing agent compound is 1 (2-10).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111178260.4A CN114171745A (en) | 2021-10-09 | 2021-10-09 | Method for optimizing carbon-supported platinum-based alloy catalyst process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111178260.4A CN114171745A (en) | 2021-10-09 | 2021-10-09 | Method for optimizing carbon-supported platinum-based alloy catalyst process |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114171745A true CN114171745A (en) | 2022-03-11 |
Family
ID=80476834
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111178260.4A Pending CN114171745A (en) | 2021-10-09 | 2021-10-09 | Method for optimizing carbon-supported platinum-based alloy catalyst process |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114171745A (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013058436A (en) * | 2011-09-09 | 2013-03-28 | Tokyo Institute Of Technology | Electrode catalyst for polymer electrolyte fuel cell and method for manufacturing the same |
CN104437474A (en) * | 2014-09-30 | 2015-03-25 | 华东师范大学 | Ordered mesoporous carbon material loaded platinum catalyst and application thereof to catalytic hydrogenation of aromatic nitro compound |
CN108075140A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of platinum base alloy elctro-catalyst |
CN109126777A (en) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | A kind of method that platinum-containing waste catalyst prepares Pt/C catalyst |
CN109546168A (en) * | 2018-11-22 | 2019-03-29 | 龙岩学院 | A kind of carbon material supported silver-colored platinum Nanoalloy composite material and preparation method |
CN110537277A (en) * | 2017-04-18 | 2019-12-03 | 田中贵金属工业株式会社 | Use in solid polymer fuel cell catalyst and its manufacturing method |
CN111640956A (en) * | 2020-06-11 | 2020-09-08 | 华南理工大学 | Method for preparing carbon-supported platinum electrocatalyst for fuel cell |
CN113113621A (en) * | 2021-02-24 | 2021-07-13 | 深圳清华大学研究院 | Preparation method and application of ordered low-platinum alloy catalyst |
-
2021
- 2021-10-09 CN CN202111178260.4A patent/CN114171745A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013058436A (en) * | 2011-09-09 | 2013-03-28 | Tokyo Institute Of Technology | Electrode catalyst for polymer electrolyte fuel cell and method for manufacturing the same |
CN104437474A (en) * | 2014-09-30 | 2015-03-25 | 华东师范大学 | Ordered mesoporous carbon material loaded platinum catalyst and application thereof to catalytic hydrogenation of aromatic nitro compound |
CN108075140A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of platinum base alloy elctro-catalyst |
CN110537277A (en) * | 2017-04-18 | 2019-12-03 | 田中贵金属工业株式会社 | Use in solid polymer fuel cell catalyst and its manufacturing method |
CN109126777A (en) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | A kind of method that platinum-containing waste catalyst prepares Pt/C catalyst |
CN109546168A (en) * | 2018-11-22 | 2019-03-29 | 龙岩学院 | A kind of carbon material supported silver-colored platinum Nanoalloy composite material and preparation method |
CN111640956A (en) * | 2020-06-11 | 2020-09-08 | 华南理工大学 | Method for preparing carbon-supported platinum electrocatalyst for fuel cell |
CN113113621A (en) * | 2021-02-24 | 2021-07-13 | 深圳清华大学研究院 | Preparation method and application of ordered low-platinum alloy catalyst |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111659419B (en) | Preparation method of carbon-supported platinum-based alloy catalyst | |
CN113600209A (en) | Method for preparing high-dispersion carbon-supported Pt-based ordered alloy catalyst and catalyst | |
CN110518257B (en) | Preparation method of carbon-supported transition metal @ Pt core-shell structure catalyst | |
CN102664275A (en) | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof | |
JPH01210037A (en) | Method of forming alloy on carrier | |
CN114094129B (en) | Preparation method of high-entropy alloy oxygen reduction electrocatalyst loaded by carbon material | |
CN106960962A (en) | A kind of platinum base of polyaniline-coated carbon carrier takes off alloy fuel cell catalyst and preparation method thereof | |
CN113707897A (en) | Anti-reversal catalyst for fuel cell and preparation method thereof | |
JPH04141236A (en) | Platinoid catalyst and its manufacturing process | |
CN111584884A (en) | Microwave preparation method of fuel cell binary alloy catalyst | |
CN110993966A (en) | Fuel cell electrocatalyst and preparation method thereof | |
CN112490453B (en) | Nitrogen-phosphorus co-doped carbon-supported platinum-cobalt-based nano alloy catalyst and preparation method and application thereof | |
CN111496270B (en) | Method for preparing nano metal platinum particles | |
JPH04135642A (en) | Platinum alloy catalyst and its production | |
CN110600752B (en) | H2Method for preparing carbon-supported Pt alloy catalyst by gas-phase thermal reduction | |
CN114171745A (en) | Method for optimizing carbon-supported platinum-based alloy catalyst process | |
CN111744473A (en) | Preparation method of Pt-based multi-component alloy nano electro-catalyst | |
CN105895931A (en) | Pt/PdNi/CNT-MnO2 methanol fuel cell catalyst and application | |
CN110611104B (en) | Low-noble metal shell catalyst prepared by reduction of polyhydroxy aldehyde ketone and preparation method thereof | |
CN109433194B (en) | Nano palladium catalyst and preparation method and application thereof | |
CN113097498A (en) | Iron-cobalt alloy nanocrystalline/nitrogen-doped carbon tube composite material and preparation method and application thereof | |
CN115254099B (en) | Method for preparing silver-palladium monoatomic catalyst by casting dealloying and post heat treatment method | |
CN116364961B (en) | Oxygen reduction catalyst, preparation method thereof and fuel cell | |
CN116565240B (en) | PtLn alloy catalyst supported by rare earth metal Ln doped NC carrier, and preparation method and application thereof | |
CN113410483B (en) | Ordering promotion preparation method of PtNi intermetallic compound catalyst of fuel cell and intermetallic compound catalyst |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220311 |