CN116742029A - Hydrogen fuel cell catalyst and preparation method thereof - Google Patents
Hydrogen fuel cell catalyst and preparation method thereof Download PDFInfo
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- CN116742029A CN116742029A CN202311006873.9A CN202311006873A CN116742029A CN 116742029 A CN116742029 A CN 116742029A CN 202311006873 A CN202311006873 A CN 202311006873A CN 116742029 A CN116742029 A CN 116742029A
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- hydrogen fuel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000000446 fuel Substances 0.000 title claims abstract description 44
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000000197 pyrolysis Methods 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 150000003057 platinum Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
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- 239000002245 particle Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
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- 239000011324 bead Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000498 ball milling Methods 0.000 claims description 9
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- 239000007789 gas Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
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- 238000010438 heat treatment Methods 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- -1 cationic platinum salt Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
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- 230000004048 modification Effects 0.000 claims description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000004966 Carbon aerogel Substances 0.000 claims description 2
- 238000001237 Raman spectrum Methods 0.000 claims description 2
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- 239000002041 carbon nanotube Substances 0.000 claims description 2
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- 125000004122 cyclic group Chemical group 0.000 claims description 2
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- 239000000956 alloy Substances 0.000 abstract description 11
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- 210000004027 cell Anatomy 0.000 description 34
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 229960001124 trientine Drugs 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- 238000001291 vacuum drying Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- PDBFXISAEVVUEJ-UHFFFAOYSA-H O[Pt](O)(O)(O)(O)O Chemical compound O[Pt](O)(O)(O)(O)O PDBFXISAEVVUEJ-UHFFFAOYSA-H 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BYFKUSIUMUEWCM-UHFFFAOYSA-N platinum;hexahydrate Chemical compound O.O.O.O.O.O.[Pt] BYFKUSIUMUEWCM-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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 hydrogen fuel cell catalyst and a preparation method thereof, wherein the hydrogen fuel cell catalyst comprises a modified carrier, the modified carrier is obtained by pyrolyzing methane and removing magnesium at high temperature through a mixture of magnesium powder and carbon powder, platinum alloy nano particles are loaded on the modified carrier and are formed by pyrolysis of a platinum-based compound, the platinum alloy nano particles comprise platinum and metal I, the weight ratio of the platinum to the metal I is 0.1-10:1, and the weight ratio of the modified carrier to the platinum alloy nano particles is 25-80:75-20. The preparation method of the hydrogen fuel cell catalyst improves the preparation process of the existing alloy catalyst, the improved process is simpler, the cost is low, the oxygen reduction activity of the alloy catalyst is better, and the stability is better.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a hydrogen fuel cell catalyst and a preparation method thereof.
Background
To protect the environment, mankind is striving to push to replace traditional energy sources with clean energy sources to achieve the "carbon neutralization" goal; proton Exchange Membrane Fuel Cells (PEMFCs) have two advantages of on-demand power generation and zero carbon emission, and are good substitutes for internal combustion engines in the field of transportation. The dependence of transportation on fossil fuel can be slowed down by hydrogen production, hydrogen storage and hydrogen utilization, and in order to promote commercialization, the durability and efficiency of the PEMFC need to be improved, and meanwhile, the manufacturing cost is reduced; it is therefore necessary to simplify the preparation process of catalytic materials of high stability and high activity. The colloid method, the precipitation method and other methods have been widely applied to the preparation of platinum-based catalysts due to the advantages of controllable size, components and the like; but there is a general problem in that a toxic and expensive surfactant or reducing agent is required. In addition, an additional step is added by removing the surfactant; as described above, there are problems in that the process for producing the alloy catalyst is complicated and the production cost is high.
Disclosure of Invention
The invention aims to overcome and supplement the defects in the prior art, and provides a hydrogen fuel cell catalyst and a preparation method thereof, which not only modify a carbon carrier to improve the stability of an alloy catalyst, but also provide a preparation method for preparing platinum-cobalt alloy particles by pyrolyzing a precursor, wherein the method can avoid covering catalytic particles by organic carbon, avoid using a surfactant and ensure the activity of the catalyst.
The technical scheme adopted by the invention is as follows:
a hydrogen fuel cell catalyst, wherein: the hydrogen fuel cell catalyst comprises a modified carrier, wherein the modified carrier is obtained by pyrolyzing a mixture of magnesium powder and carbon powder at a high temperature and removing magnesium, platinum alloy nano particles are loaded on the modified carrier, the platinum alloy nano particles are formed by pyrolyzing a platinum-based compound, the platinum alloy nano particles comprise platinum and metal I, the weight ratio of the platinum to the metal I is 0.1-10:1, and the weight ratio of the modified carrier to the platinum alloy nano particles is 25-80:75-20 parts; the metal one is selected from one of iron, cobalt, nickel, copper and palladium.
Preferably, the hydrogen fuel cell catalyst, wherein: the average particle diameter of the platinum alloy nano particles is 2-20 nm.
A method of preparing a hydrogen fuel cell catalyst, wherein: the method comprises the following steps:
s1, modification of a carrier: mixing magnesium powder and carbon powder according to a mass ratio of 30-10:70-90, placing the mixed powder in a tube furnace, continuously introducing methane into the tube furnace, controlling the temperature in the tube furnace to rise to 1400-2800 ℃ at a speed of 2-30 ℃/min, preserving heat for 1-18h, pyrolyzing the mixed powder at a high temperature to obtain powder with a graphitized deposited surface layer, pyrolyzing methane to obtain powder with a graphitized surface layer, wherein if the temperature is too low or the constant temperature is too short, the efficiency of pyrolyzing methane is too low, if the temperature is too high or the constant temperature is too long, the energy consumption is too high, and the cost for preparing the catalyst is increased, so that the further preferable temperature is 1600-2000 ℃, the constant temperature is 2-6h, and removing metal magnesium from the powder to obtain a mesoporous modified carrier;
s2, synthesizing a precursor: weighing platinum salt and metal one salt, adding the platinum salt into water until the platinum salt is dissolved to obtain a platinum solution, adding the metal one salt into a nitrogen-containing organic matter to be dissolved to form a metal one solution, mixing the platinum solution and the metal one solution for reaction, washing and drying to obtain a precursor;
s3, carrying: adding zirconium beads into the mixture obtained by mixing the precursor, the modified carrier and the absolute ethyl alcohol, ball milling and sieving the mixture, and stirring the mixture to remove the absolute ethyl alcohol to obtain a solidified product;
s4, alloying: and placing the solidified product in a tubular furnace, introducing gas I into the tubular furnace for pyrolysis, and then introducing gas II into the tubular furnace for calcination to obtain the hydrogen fuel cell catalyst.
Preferably, the preparation method of the hydrogen fuel cell catalyst comprises the following steps: in the step S1, carbon powder is selected from one of acetylene black, conductive carbon black, carbon nano tube, graphene, mesoporous carbon, carbon aerogel and hollow carbon; the specific surface area of the modified carrier is 200-3000 m 2 and/G, wherein the D/G ratio in the Raman spectrum curve of the modified carrier is 0.8-1.4.
Preferably, the preparation method of the hydrogen fuel cell catalyst comprises the following steps: in the step S1, the metal magnesium is removed from the powder specifically: adding the powder into acid liquor, controlling the reaction temperature to be 0-90 ℃, the reaction time to be 0.5-24h, and repeating the steps for 1-5 times until the content of magnesium metal is reduced to below 10ppm, wherein the acid liquor is one or more of sulfuric acid, nitric acid, hydrochloric acid and perchloric acid with the concentration of 0.1-10M, and the mass ratio of the powder to the acid liquor is 0.001-0.6:1.
preferably, the preparation method of the hydrogen fuel cell catalyst comprises the following steps: the platinum salt in the step S2 is an anionic or cationic platinum salt which dissociates to obtain platinum, the metal one salt is a salt which can form a cationic complex or an anionic complex with a nitrogen-containing organic matter, the nitrogen-containing organic matter is selected from one of single-chain carbon and branched carbon with the carbon number of more than 2, and the single-chain carbon and the branched carbon do not contain cyclic carbon; the mol ratio of the platinum salt to the metal one is 1-5:5-1.
The platinum salt can dissociate into platinum-containing anions or cations, such as chloroplatinic acid (H) 2 PtCl 6 Can dissociate to obtain an anion PtCl 6 2- ) Potassium chloroplatinate (K) 2 PtCl 6 Can dissociate to obtain an anion PtCl 6 2- ) HexahydroxyPlatinum acid radical H 2 Pt(OH) 6 Can be dissociated to give anions (Pt (OH) 6 2- ) Etc.;
the salt of the metal one may be a metal salt other than platinum salt, which satisfies that the metal ion can form a cationic complex or an anionic complex with an organic matter containing nitrogen, such as a nitrate, nitrite, chloride, bromide, sulfate, acetate, acetylacetonate, oxalate, carbonyl salt, or the like formed with iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) palladium (Pd), or the like, and further such as a metal salt of cobalt nitrate, cobalt chloride, cobalt acetylacetonate, or the like.
The nitrogen-containing organic matter may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, etc.
Preferably, the preparation method of the hydrogen fuel cell catalyst comprises the following steps: the mass ratio of the platinum salt to the water in the step S2 is 1:50-150, the reaction temperature is 0-50 ℃, and the reaction time is 0.5-8h.
Preferably, the preparation method of the hydrogen fuel cell catalyst comprises the following steps: in the step S3, the mass ratio of the precursor, the modified carrier, the absolute ethyl alcohol and the zirconium beads is 0.5-2.5:1:50-300:50-300, wherein the ball milling rotating speed is 200-500 rpm, and the ball milling time is 2-18h; the reaction temperature in the ethanol removal process is 0-50 ℃.
Preferably, the preparation method of the hydrogen fuel cell catalyst comprises the following steps: the pyrolysis temperature in the step S4 is 300-600 ℃, the pyrolysis time is 0.5-1.5h, the heating rate is 5-10 ℃ per minute, and one or more gases selected from hydrogen, ammonia, nitrogen and argon are introduced into the tubular furnace.
Preferably, the preparation method of the hydrogen fuel cell catalyst comprises the following steps: the calcination temperature in the step S4 is 650-1050 ℃, the calcination time is 1-18h, and the gas II introduced into the tube furnace is one or more selected from hydrogen, ammonia, nitrogen and argon.
The invention has the advantages that:
(1) The preparation method of the hydrogen fuel cell catalyst improves the preparation process of the existing alloy catalyst, the improved process is simpler, the cost is low, the oxygen reduction activity of the alloy catalyst is better, and the stability is better.
(2) The hydrogen fuel cell catalyst of the invention utilizes the platinum-containing anions and metal-containing cations or the platinum-containing cations and metal-containing anions to carry out accurate assembly through electrostatic action without improving the dispersibility of the metal-I through expensive surfactants; the catalyst precursor avoids the use of chlorine-containing anions and reduces the possibility of poisoning the catalyst by chloride ions.
(3) According to the hydrogen fuel cell catalyst, the catalyst precursor adopts the single-chain organic amine without benzene ring, so that a large amount of carbon is prevented from being coated on the surface of the catalytic particles after pyrolysis, the exposure of catalytic active sites is facilitated, and the activity of the catalyst is improved; the organic amine contains rich nitrogen atoms, and can enter catalytic particles in the pyrolysis process, which possibly causes shortening of the bond length of Pt-Pt bonds, and the compressive strain caused by the organic amine helps to improve the catalytic activity and stability of the catalyst.
(4) According to the hydrogen fuel cell catalyst, the surface of the modified carbon carrier is provided with a layer of graphitized carbon, so that carbon corrosion reaction caused by oxidation can be delayed, and the abundant mesopores are beneficial to slowing down aggregation and growth of alloy nano particles in the high-temperature pyrolysis process.
Drawings
Fig. 1 is a TEM photograph of the platinum cobalt alloy catalyst in example 2.
FIG. 2 is a graph of ORR polarization curves for example 2 and comparative examples 1-3.
FIG. 3 is a graph of ORR polarization curves before and after 30000 cycles of cyclic voltammetry for the catalyst of example 2.
Fig. 4 is a powder X-ray diffraction pattern of a platinum cobalt compound precursor composed of a platinum anion and a cobalt cation in example 2.
Fig. 5 is a powder X-ray diffraction pattern of the platinum cobalt alloy catalyst in example 2 and comparative example 1.
Fig. 6 is a graph showing polarization curves of fuel cells (single cells) produced after the catalyst-prepared membrane electrode of example 2 and comparative example 4.
Fig. 7 is a graph showing the polarization curve and the power density-current density curve measured for a fuel cell (cell) after the catalyst of example 3 was prepared.
Fig. 8 is a TEM element diagram of the platinum cobalt alloy catalyst in example 2.
Detailed Description
The invention will be further illustrated with reference to specific examples.
EXAMPLE 1 modification of carbon support
S1, modifying a carrier: mixing magnesium powder and carbon powder according to a mass ratio of 15:85, placing the mixed powder into a tube furnace, continuously introducing methane into the tube furnace, controlling the temperature in the tube furnace to rise to 1800 ℃ at a speed of 10 ℃/min, preserving heat for 10 hours, pyrolyzing the mixed powder at a high temperature to obtain powder with a graphitized deposited surface layer, adding the powder into 0.1M dilute nitric acid solution, controlling the reaction temperature to be 60 ℃, controlling the reaction time to be 12 hours, repeating the steps for 2 times until the content of magnesium metal is reduced to below 10ppm, and obtaining a mesoporous modified carrier, wherein the mass ratio of the powder to acid liquor is 0.01:1.
EXAMPLE 2 Synthesis of platinum cobalt Compound
S2, weighing 0.294 and g cobalt nitrate hexahydrate, slowly adding the cobalt nitrate hexahydrate into 30mL ethylenediamine, and performing ultrasonic treatment until the cobalt nitrate hexahydrate is completely dissolved; 10mL of ultrapure water was measured for dissolving 0.296g of hexahydroxyplatinic acid, and the two solutions were mixed to form [ Co (en) ] 3 ][Pt(OH) 6 ](en represents ethylenediamine) precipitate, stirring at room temperature for 4 hr, washing the reaction product with 100mL anhydrous ethanol for 5 times, drying the filtered solid in a vacuum drying oven at 25deg.C for one night, and grinding with mortar to obtain platinum cobalt compound precursor;
s3, crushing a precursor and a carrier: the solid powder of the platinum cobalt compound obtained above was weighed with the modified support of example 1 according to a mass ratio of 3.146, according to a pure platinum accounting for 46% of the total mass of all solids (carbon+platinum+cobalt): 1, premixing, grinding for 10min, then transferring the mixed powder into a ball milling tank, adding zirconium beads with the diameter of 2mm, and simultaneously adding ethanol, so that the mixed powder: zirconium beads: the mass ratio of the ethanol is 20:50:30; firstly, pretreating the mixed solution for 10min under 400rpm of a ball mill, then immediately reducing to 200 rpm, keeping for 12h, and cooling; sieving the mixed liquid with a sieve with the specification of 400 meshes, transferring the sieved mixture into a beaker, and continuously stirring the mixture with a stirring rod until the absolute ethyl alcohol is completely volatilized, and retaining the products of the compound and the carbon carrier to obtain a solidified product;
s4, pyrolysis and calcination: placing the solidified material into a porcelain boat, and placing the porcelain boat into a tube furnace for calcination; firstly heating to 500 ℃ and preserving heat for 1.5h, so that the compound carried on the carbon carrier is fully pyrolyzed, continuously heating to 800 ℃ and preserving heat for 1h, alloying platinum and cobalt in the process, naturally cooling to room temperature, continuously introducing nitrogen in the whole pyrolysis process, and calcining to obtain the platinum-cobalt alloy catalyst with the platinum content of 45.9%.
EXAMPLE 3 Synthesis of platinum cobalt Compound
S2, weighing 0.296 and g cobalt nitrate hexahydrate, slowly adding the cobalt nitrate hexahydrate into 30mL diethylenetriamine, performing ultrasonic treatment until the cobalt nitrate hexahydrate is completely dissolved, weighing 10mL ultrapure water for dissolving 0.291g of hexahydroxy platinum acid, and mixing the two solutions to form [ Co (dien) 3 ][Pt(OH) 6 ](dien represents diethylenetriamine) precipitate, stirring continuously at room temperature for 4 hours, washing the reaction product with 100mL of absolute ethyl alcohol each time after the reaction is completed, repeating for 5 times, placing the solid obtained by filtration in a vacuum drying oven at 25 ℃ for drying overnight, and grinding by using a mortar to obtain a platinum cobalt compound precursor;
s3, crushing a precursor and a carrier: the solid powder of the platinum-cobalt compound obtained above was weighed according to a mass ratio of pure platinum to the modified carrier of example 1 of 3.921:1, premixing, grinding for 10min, then transferring the mixed powder into a ball milling tank, adding zirconium beads with the diameter of 2mm, and simultaneously adding ethanol, so that the mixed powder: zirconium beads: the mass ratio of the ethanol is 20:50:30; firstly, pretreating the mixed solution for 10min under 400rpm of a ball mill, then immediately reducing to 200 rpm, keeping for 12h, and cooling; and (3) carrying: sieving the mixed liquid with a sieve with the specification of 400 meshes, transferring the sieved mixture into a beaker, and continuously stirring the mixture with a stirring rod until the absolute ethyl alcohol is completely volatilized, and retaining the product of the compound and the carbon carrier to obtain a solidified substance;
s4, pyrolysis and calcination: the solidified substance is placed in a porcelain boat and is put in a tube furnace for calcination, the temperature is firstly raised to 500 ℃ and kept for 1.5 hours, so that the compound carried on the carbon carrier is fully pyrolyzed, the temperature is continuously raised to 800 ℃ and kept for 1 hour, and the process enables the platinum and cobalt to be alloyed. Naturally cooling to room temperature, continuously introducing nitrogen in the whole pyrolysis process, and calcining to obtain the platinum-cobalt alloy catalyst with the platinum content of 45.6%.
EXAMPLE 4 Synthesis of platinum cobalt Compound
S2, weighing 0.295g of cobalt nitrate hexahydrate, slowly adding the cobalt nitrate hexahydrate into 30mL of triethylene tetramine, carrying out ultrasonic treatment until the cobalt nitrate hexahydrate is completely dissolved, weighing 10mL of ultrapure water for dissolving 0.293g of hexahydroxy platinum acid, and mixing the two solutions to form [ Co (trien) 3 ][Pt(OH) 6 ](trien represents triethylene tetramine) precipitate is continuously stirred for 4 hours at room temperature, after the reaction is finished, the reaction product is washed by 100mL of absolute ethyl alcohol for 5 times each time, the solid obtained by filtration is placed in a vacuum drying oven at 25 ℃ for drying overnight, and then a mortar is used for grinding, so that a platinum cobalt compound precursor is obtained;
s3, crushing a precursor and a carrier: the solid powder of the platinum cobalt compound obtained above was weighed with the modified support of example 1 according to a mass ratio of 4.672, according to a pure platinum accounting for 46% of the total mass of all solids (carbon+platinum+cobalt): 1, premixing, grinding for 10min, then transferring the mixed powder into a ball milling tank, adding zirconium beads with the diameter of 2mm, and simultaneously adding ethanol, so that the mixed powder: zirconium beads: the mass ratio of the ethanol is 20:50:30; firstly, pretreating the mixed solution for 10min under 400rpm of a ball mill, then immediately reducing to 200 rpm, keeping for 12h, and cooling; and (3) carrying: sieving the mixed liquid with a sieve with the specification of 400 meshes, transferring the sieved mixture into a beaker, and continuously stirring the mixture with a stirring rod until the absolute ethyl alcohol is completely volatilized, and retaining the product of the compound and the carbon carrier to obtain a solidified substance;
s4, pyrolysis and calcination: placing the solidified substance into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 500 ℃ and preserving heat for 1.5 hours, enabling the compound carried on the carbon carrier to be pyrolyzed sufficiently, continuously heating to 800 ℃ and preserving heat for 1 hour, enabling the platinum and cobalt to be alloyed, naturally cooling to room temperature, continuously introducing nitrogen in the whole pyrolysis process, and obtaining the platinum and cobalt alloy catalyst with the platinum content of 44.9% after calcination.
Comparative example 1: the procedure was the same as in example 2, except that the modified carbon support was replaced with a commercially available carbon support.
Comparative example 2: the precursor [ Co (en) ] obtained was obtained except that 0.296g of hexahydroxy platinic acid of example 2 was replaced with 0.516g of chloroplatinic acid 3 ][PtCl 6 ]The mass ratio of the modified carbon carrier to the modified carbon carrier is replaced by 3.804:1, the rest of the steps are the same as in example 2, and finally a platinum cobalt alloy catalyst with a platinum content of 45.8% is obtained.
Comparative example 3: the precursor [ Co (phen) ] obtained was obtained except that ethylenediamine of example 2 was replaced with an aqueous solution containing 1, 10-phenanthroline 3 ][Pt(OH) 6 ](phen stands for 1, 10-phenanthroline) to modified carbon support mass ratio is replaced by 5.271:1, the rest of the steps are the same as in example 2, and finally a platinum cobalt alloy catalyst with a platinum content of 43.6% is obtained.
Comparative example 4: modified carbon Carrier (0.261 g), H 2 PtCl 6 ·6H 2 O（0.533g）、Co(NO 3 ) 2 ·6H 2 O (0.3 g) was added to 400mL polyethylene glycol (PEG) and sonicated to disperse it uniformly. 3.71g NaBH 4 Slowly adding into the mixture, and continuously stirring for 40min; after the mixture is heated to 45 ℃, stirring is continued for 4 hours; dilute nitric acid (5 wt% in deionized water) was added to the mixture to render the mixture acidic; repeatedly washing the precipitate obtained by filtering the mixture, and vacuum drying overnight; placing the dried powder in a tube furnace, heating to 500 ℃ and preserving heat for 1.5h, continuously heating to 800 ℃ and preserving heat for 1h, and alloying platinum and cobalt in the process; naturally cooling to room temperature, and continuously introducing nitrogen in the whole pyrolysis process; the platinum-cobalt alloy catalyst completely free of nitrogen elements (the mass ratio of pure platinum to the whole catalyst is 46.1%) can be obtained after calcination.
The catalysts prepared in examples 2 to 4 and comparative examples 1 to 4 were subjected to catalytic activity evaluation:
1. preparation of working electrode
5mg of the catalyst was weighed into a glass bottle, 900. Mu.L of a mixed solution of ethanol and water (v: v=1:1) was added, 100. Mu.L of 5wt% Nafion (DuPont) was added, and after ultrasonic homogenization, an ink in which the catalyst was uniformly dispersed was obtained, 5. Mu.L of the ink was removed, and uniformly coated on a mirror-polished glass carbon surface, and dried naturally at room temperature for subsequent electrochemical measurement.
2. Electrochemical measurement
Electrochemical measurements were performed using a pin electrochemical workstation in a three electrode configuration, using a five port glass cell as a container for electrolyte; the catalyst-coated glassy carbon electrode was used as a working electrode. The geometric area of the electrode exposed to the electrolyte was 0.196cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Adopting Hg/HgO electrode and Pt wire as reference electrode and counter electrode; calibration of Hg/HgO electrode in 0.1M perchloric acid solution, the conversion relation of Hg/HgO electrode and Reversible Hydrogen Electrode (RHE) is E RHE = E Hg/HgO +0.711; cyclic Voltammetry (CV) is carried out by introducing high-purity O 2 Or N 2 After 30min of gas, the scanning speed is 50 mV/s; linear Sweep Voltammetry (LSV) is carried out using RDE at O 2 In a saturated 0.1M perchloric acid solution at 1600rpm and at a scan rate of 1mV/s; during the measurement, O is maintained above the electrolyte 2 Or N 2 Is sufficient to flow; at N 2 Collecting background current in saturated electrolyte and applying the current to O 2 The lower polarization curve is corrected to eliminate the influence of the capacitance current.
3. Fuel cell membrane electrode fabrication
Weighing 0.2g of alloy catalyst, adding a mixed solution containing 10mL of ultrapure water, 10mL of isopropanol and 1.2mL of ionomer (5% by mass of perfluorosulfonic acid resin solution), stirring for 10min, and crushing cells for 30min to form uniform catalyst ink; uniformly scraping ink on a proton exchange membrane to serve as a cathode; similarly, 0.2g of a commercially available platinum carbon catalyst (mass fraction of platinum: 60%, zhuang Xinmo Feng Co.) was weighed, a mixed solution containing 10mL of ultrapure water, 10mL of isopropyl alcohol and 1.2mL of ionomer (mass fraction of 20% perfluorosulfonic acid resin solution) was added, stirred for 10min, the cells were crushed for 30min to form a uniform catalyst ink, and the catalyst ink was coated on the back surface of the above film as an anode, and vacuum-dried at 60℃for 2h to serve as a film electrode for test.
FIG. 1 is a TEM micrograph of the platinum cobalt alloy catalyst of example 2, on a scale of 10nm, showing a catalyst particle size ranging from 2 to 5 nm.
FIG. 2 shows 0.1M HClO saturated with oxygen 4 In solution, the rotating disk was turned at 1600rpm and the catalysts prepared by the example 2, comparative example 1, comparative example 2, comparative example 3 protocol were compared to commercial platinum carbon using a scan rate of 5 mV/s by subtracting the nitrogen background from the main plot of the ORR polarization curve; first, the catalyst of example 2 has an activity superior to that of comparative example 1 because the modified carbon support effectively inhibits the growth of catalytic particles during calcination, effectively enhancing the activity of the catalyst; secondly, the activity of the catalyst of example 2 is superior to that of comparative example 2 because the poisoning effect of chloride ions introduced by platinum salt in comparative example 2 on the catalyst reduces the activity of the catalyst, and furthermore, the activity of the catalyst of example 2 is superior to that of comparative example 3 because benzene rings in nitrogen-containing ligands form carbon coated on the surfaces of catalytic particles after pyrolysis, reducing the active sites of the catalyst and further reducing the catalytic activity; finally, the alloy catalyst activity is superior to commercial platinum carbon catalysts.
FIG. 3 shows a main graph of ORR polarization curves of the catalyst prepared in example 2 before and after 30000 cycles of cyclic voltammetry, and experimental results show that the catalyst performance attenuation is reduced by less than 10%, and the catalyst has good catalytic stability.
FIG. 4 shows a powder X-ray diffraction pattern of a platinum cobalt compound precursor composed of a platinum anion and a cobalt cation in example 2.
Fig. 5 shows powder X-ray diffraction patterns of the platinum cobalt alloy catalysts of example 2 and comparative example 1, calculated from the half-widths of the main peaks (41.6 °), fitted, indicating that the pretreated carbon support can inhibit the growth of catalytic particles during high temperature calcination.
Fig. 6 shows polarization curves measured for a fuel cell (cell) made of membrane electrode, and it is understood from the graph that the catalyst of example 2 has better activity than the catalyst of comparative example 4 because of nitrogen doping, which improves the activity of catalytic particles, indicating that the alloy catalyst obtained by the pyrolysis method is superior to the alloy catalyst prepared by the conventional process.
Fig. 7 shows the polarization curve and the power density-current density curve measured for a fuel cell (cell) made of membrane electrode.
FIG. 8 shows a TEM element diagram of the platinum-cobalt alloy catalyst of example 2, which is shown on a scale of 100nm, and shows that the platinum element and the cobalt element are rich in nitrogen.
TABLE 1 evaluation results of Membrane electrode Activity
Table 1 shows the membrane electrode made of the catalyst and the fuel cell assembled with other devices measured at 1A/cm 2 And 2A/cm 2 The greater the voltage, the better the activity of the catalyst; in addition, the power density of the membrane electrode was calculated at a voltage level of 0.65V, and in general, the higher the power density, the better the activity of the catalyst, and the catalytic activities of examples 3 and 4 were superior to those of comparative examples 1 to 4.
TABLE 2 evaluation results of Membrane electrode stability
Table 2 shows the polarization curves of the fuel cells measured after accelerated aging, calculated at a current density of 1A/cm, with reference to the DOE published test method for durability of fuel cells 2 And 2A/cm 2 In general, the smaller the degree of loss, the better the durability of the catalyst, and the durability of example 2 is better than that of comparative examples 2 and 4.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (10)
1. A hydrogen fuel cell catalyst characterized by: the hydrogen fuel cell catalyst comprises a modified carrier, wherein the modified carrier is obtained by pyrolyzing a mixture of magnesium powder and carbon powder at a high temperature and removing magnesium, platinum alloy nano particles are loaded on the modified carrier, the platinum alloy nano particles are formed by pyrolyzing a platinum-based compound, the platinum alloy nano particles comprise platinum and metal I, the weight ratio of the platinum to the metal I is 0.1-10:1, and the weight ratio of the modified carrier to the platinum alloy nano particles is 25-80:75-20 parts; the metal one is selected from one of iron, cobalt, nickel, copper and palladium.
2. The hydrogen fuel cell catalyst according to claim 1, characterized in that: the average particle diameter of the platinum alloy nano particles is 2-20 nm.
3. A method for producing a hydrogen fuel cell catalyst according to any one of claims 1 to 2, characterized in that: the method comprises the following steps:
s1, modification of a carrier: mixing magnesium powder and carbon powder according to a mass ratio of 30-10:70-90, placing the mixed powder in a tube furnace, continuously introducing methane into the tube furnace, controlling the temperature in the tube furnace to rise to 1400-2800 ℃ at a speed of 2-30 ℃/min, and preserving heat for 1-18h to enable the mixed powder to be pyrolyzed at a high temperature to obtain powder with a graphitized deposited surface layer, and removing metal magnesium from the powder to obtain a mesoporous modified carrier;
s2, synthesizing a precursor: weighing platinum salt and metal one salt, adding the platinum salt into water until the platinum salt is dissolved to obtain a platinum solution, adding the metal one salt into a nitrogen-containing organic matter to be dissolved to form a metal one solution, mixing the platinum solution and the metal one solution for reaction, washing and drying to obtain a precursor;
s3, carrying: adding zirconium beads into a mixture obtained by mixing a precursor, a modified carrier and absolute ethyl alcohol, performing ball milling and sieving, and stirring the mixture to remove the absolute ethyl alcohol to obtain a solidified product;
s4, alloying: and placing the solidified product in a tubular furnace, introducing gas I into the tubular furnace for pyrolysis, and then introducing gas II into the tubular furnace for calcination to obtain the hydrogen fuel cell catalyst.
4. A method for producing a hydrogen fuel cell catalyst according to claim 3, characterized in that: in the step S1, carbon powder is selected from one of acetylene black, conductive carbon black, carbon nano tube, graphene, mesoporous carbon, carbon aerogel and hollow carbon; the specific surface area of the modified carrier is 200-3000 m 2 and/G, wherein the D/G ratio in the Raman spectrum curve of the modified carrier is 0.8-1.4.
5. A method for producing a hydrogen fuel cell catalyst according to claim 3, characterized in that: in the step S1, the metal magnesium is removed from the powder specifically: adding the powder into acid liquor, controlling the reaction temperature to be 0-90 ℃, the reaction time to be 0.5-24h, and repeating the steps for 1-5 times until the content of magnesium metal is reduced to below 10ppm, wherein the acid liquor is one or more of sulfuric acid, nitric acid, hydrochloric acid and perchloric acid with the concentration of 0.1-10M, and the mass ratio of the powder to the acid liquor is 0.001-0.6:1.
6. a method for producing a hydrogen fuel cell catalyst according to claim 3, characterized in that: the platinum salt in the step S2 is an anionic or cationic platinum salt which dissociates to obtain platinum, the metal one salt is a salt which can form a cationic complex or an anionic complex with a nitrogen-containing organic matter, the nitrogen-containing organic matter is selected from one of single-chain carbon and branched carbon with the carbon number of more than 2, and the single-chain carbon and the branched carbon do not contain cyclic carbon; the mol ratio of the platinum salt to the metal one is 1-5:5-1.
7. A method for producing a hydrogen fuel cell catalyst according to claim 3, characterized in that: the mass ratio of the platinum salt to the water in the step S2 is 1:50-150, the reaction temperature is 0-50 ℃, and the reaction time is 0.5-8h.
8. A method for producing a hydrogen fuel cell catalyst according to claim 3, characterized in that: in the step S3, the mass ratio of the precursor, the modified carrier, the absolute ethyl alcohol and the zirconium beads is 0.5-2.5:1:50-300:50-300, wherein the ball milling rotating speed is 200-500 rpm, and the ball milling time is 2-18h; the reaction temperature in the ethanol removal process is 0-50 ℃.
9. A method for producing a hydrogen fuel cell catalyst according to claim 3, characterized in that: the pyrolysis temperature in the step S4 is 300-600 ℃, the pyrolysis time is 0.5-1.5h, the heating rate is 5-10 ℃ per minute, and one or more gases selected from hydrogen, ammonia, nitrogen and argon are introduced into the tubular furnace.
10. A method for producing a hydrogen fuel cell catalyst according to claim 3, characterized in that: the calcination temperature in the step S4 is 650-1050 ℃, the calcination time is 1-18h, and the gas II introduced into the tube furnace is one or more selected from hydrogen, ammonia, nitrogen and argon.
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| CN111097447A (en) * | 2018-10-29 | 2020-05-05 | 中国石油天然气股份有限公司 | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen |
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| CN114430048A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof, membrane electrode and direct liquid fuel cell |
| CN115954493A (en) * | 2023-01-07 | 2023-04-11 | 中自环保科技股份有限公司 | Method for improving activity and stability of supported platinum-based catalyst |
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| CN111097447A (en) * | 2018-10-29 | 2020-05-05 | 中国石油天然气股份有限公司 | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen |
| CN111244484A (en) * | 2020-01-17 | 2020-06-05 | 重庆大学 | Preparation method of sub-nano platinum-based ordered alloy |
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