CN107799778B - Carbon fiber supported noble metal catalyst and preparation method and application thereof - Google Patents
Carbon fiber supported noble metal catalyst and preparation method and application thereof Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 123
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 111
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000010355 oscillation Effects 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 9
- 229940117927 ethylene oxide Drugs 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- -1 orthosilicate ester Chemical class 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a carbon fiber supported noble metal catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) introducing carbon-containing gas and oxygen into the catalyst, and reacting at 500-1000 ℃ for 18-32h to prepare carbon fiber; (2) adding a stabilizer and a reducing agent into the noble metal solution, and reacting for 2-20h at 60-120 ℃ to obtain noble metal sol; (3) soaking carbon fibers in the noble metal sol by adopting an isometric soaking method and/or an excess soaking method, adjusting the pH value to 4-5, heating and stirring, and assisting ultrasonic oscillation reaction for 5-20 hours; (4) and placing the impregnated carbon fibers in inert gas for calcining to obtain the carbon fiber supported noble metal catalyst. The preparation method has simple and convenient process, and the carbon fiber-supported noble metal catalyst with excellent catalytic performance is prepared by taking the carbon fiber as the carbon base under the synergistic cooperation of the steps.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and relates to a carbon fiber supported noble metal catalyst, and a preparation method and application thereof.
Background
In recent years, carbon fiber has been a research hotspot because of its excellent physicochemical properties such as large specific surface area, high mechanical strength, good electrical conductivity, good chemical stability, and the like, and is applied to the electrochemical field as a carbon-based material.
The surface of the noble metal is easy to adsorb reactants, the adsorption force is moderate, an intermediate active compound is favorably formed, the chemical reaction speed can be accelerated, the noble metal does not participate in the reaction, and the noble metal has the characteristics of high temperature resistance, oxidation resistance, corrosion resistance and the like, and becomes an important catalytic material to be applied to the field of catalysts.
The impregnation method is one of the commonly used methods for preparing a solid catalyst based on the principle that a metal salt solution is adsorbed or stored in a capillary tube of a support and permeates into the inner surface. The method generally puts the carrier into the metal salt solution, when the impregnation reaches the equilibrium, separates the carrier, removes the excessive solution, and then prepares the catalyst through the treatment processes of drying, calcining, activating, etc. The impregnation method is simple and low in cost, and is a main method for preparing the supported metal catalyst in industry at present.
CN102658133A discloses a preparation method of an activated carbon supported noble metal catalyst, which comprises the steps of mixing an activated carbon carrier with a nitrate solution or a chloride aqueous solution containing noble metals, stirring at 25-90 ℃ for 2-6h, adding an alkaline aqueous solution at 25-80 ℃ to adjust the pH value of a reaction solution to 6-9, stirring at 25-80 ℃ for 0.5-4h under heat preservation to obtain slurry, and carrying out aftertreatment on the slurry to obtain the activated carbon supported noble metal catalyst. However, the method has harsh conditions and poor dispersion effect of the activated carbon, so that the catalytic performance of the noble metal is reduced and the service life is short.
CN103691428A discloses a method for preparing a carbon-supported noble metal catalyst, which comprises the step of reducing a noble metal precursor-loaded carrier obtained by an impregnation method by atmospheric pressure cold plasma to obtain a high-performance carbon-supported noble metal catalyst. However, the method has complex process, high cost and low yield.
Therefore, the preparation method of the noble metal catalyst with simple process and low cost is provided, the noble metal catalyst with good catalytic performance and high loading capacity is obtained, and the method has important significance in the field of electrochemical catalysis.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a carbon fiber supported noble metal catalyst and a preparation method and application thereof, the method has simple process and lower cost, the prepared noble metal catalyst takes carbon fibers as a carrier, high-content noble metal is supported, and the catalytic activity can reach 99.5%.
In a first aspect, the invention provides a preparation method of a carbon fiber supported noble metal catalyst, which comprises the following steps:
(1) introducing carbon-containing gas and oxygen into the catalyst, and reacting at 500-1000 ℃ for 18-32h to prepare carbon fiber;
(2) adding a stabilizer and a reducing agent into the noble metal solution, and reacting for 2-20h at 60-120 ℃ to obtain noble metal sol;
(3) soaking carbon fibers in the noble metal sol by adopting an isometric soaking method and/or an excess soaking method, adjusting the pH value to 4-5, heating and stirring, and assisting ultrasonic oscillation reaction for 5-20 hours;
(4) and placing the impregnated carbon fibers in inert gas for calcining to obtain the carbon fiber supported noble metal catalyst.
According to the invention, the carbon fiber with a regular structure, a small particle size and a large specific surface area is obtained by adjusting the volume of the carbon-containing gas, the carbon fiber uniformly loaded with noble metal is obtained by adjusting the mass ratio of the carbon-containing gas to the noble metal solution, and under the synergistic cooperation of the steps, the yield of the prepared carbon fiber loaded with noble metal reaches 99.8%, and the catalytic performance of the catalyst reaches 99.5%.
Preferably, the catalyst in step (1) comprises any one of or a combination of at least two of gamma-alumina supported nickel, gamma-alumina supported iron or gamma-alumina supported nickel-iron alloy, such as a combination of gamma-alumina supported nickel and gamma-alumina supported iron, a combination of gamma-alumina supported nickel and gamma-alumina supported nickel-iron alloy, or a combination of gamma-alumina supported iron and gamma-alumina supported nickel-iron alloy, preferably gamma-alumina supported nickel-iron alloy.
Preferably, the volume ratio of the carbon-containing gas to the oxygen gas in step (1) is (1-5):1, and may be, for example, 1:1, 2:1, 3:1, 4:1 or 5:1, preferably 3: 1.
Preferably, the carbon-containing gas of step (1) comprises a combination of at least two of methane, ethylene or carbon monoxide, and may be, for example, a combination of methane and ethylene, a combination of methane and carbon monoxide, a combination of ethylene and carbon monoxide, or a combination of methane, ethylene and carbon monoxide, preferably a combination of methane, ethylene and carbon monoxide;
preferably, the volume ratio of methane, ethylene and carbon monoxide is (1-3): 1-2):2, and may be, for example, 1:1:2, 2:1:2, 3:1:2, 1:2:2, 2:2:2 or 3:2:2, preferably 2:1: 2.
Preferably, the reaction temperature in step (1) is 500-.
Preferably, the reaction time in step (1) is 20-30h, for example, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h, preferably 25 h.
Preferably, the carbon fiber of step (1) has a particle size of 10 to 50nm, and may be, for example, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 28nm, 30nm, 32nm, 35nm, 38nm, 40nm, 42nm, 45nm, 48nm or 50 nm.
Preferably, the specific surface area of the carbon fiber in the step (1) is 200-1000m2A/g, which may be, for example, 200m2/g、250m2/g、300m2/g、350m2/g、400m2/g、450m2/g、500m2/g、550m2/g、600m2/g、650m2/g、700m2/g、750m2/g、800m2/g、850m2/g、900m2/g、950m2In g or 1000m2/g。
Preferably, the noble metal of step (2) comprises any one or a combination of at least two of platinum, ruthenium, palladium, rhodium, iridium or gold, preferably platinum.
Preferably, the stabilizer in step (2) comprises any one or a combination of at least two of polyethylene glycol, polyvinyl pyridine, polyvinyl alcohol, orthosilicate ester or sodium citrate, preferably polyethylene glycol.
Preferably, the reducing agent in step (2) comprises any one or a combination of at least two of hydrogen, acetaldehyde, carbon monoxide, polyethylene glycol or polyvinylpyrrolidone, preferably acetaldehyde.
Preferably, the reaction temperature in step (2) is 80-110 ℃, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃ or 110 ℃, preferably 100 ℃.
Preferably, the reaction time in step (2) is 5-15h, for example, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, preferably 8 h.
Preferably, the mass ratio of the carbon fiber to the noble metal sol in the step (3) is 10 (1-5), for example, 10:1, 10:2, 10:3, 10:4 or 10:5, preferably 10 (3-4).
Preferably, the heating temperature in step (3) is 40-80 deg.C, such as 40 deg.C, 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, 72 deg.C, 75 deg.C, 78 deg.C or 80 deg.C, preferably 60 deg.
Preferably, the reaction time in step (3) is 8-15h, for example 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, preferably 10 h.
Preferably, the inert gas in step (4) includes any one or a combination of at least two of nitrogen, helium or argon, and may be, for example, a combination of nitrogen and helium, a combination of nitrogen and argon, a combination of helium and argon or a combination of nitrogen, helium and argon, preferably argon.
Preferably, the temperature of the calcination in step (4) is 200-.
Preferably, the calcination time in step (4) is 3 to 5 hours, and may be, for example, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours, 4 hours, 4.1 hours, 4.2 hours, 4.3 hours, 4.4 hours, 4.5 hours, 4.6 hours, 4.7 hours, 4.8 hours, 4.9 hours or 5 hours, preferably 4 hours.
Preferably, step (1) is followed by a step of purifying and activating the carbon fibers.
Preferably, said purified and activated carbon fibers comprise in particular:
(1') washing the carbon fiber in NaOH solution for 3-5h, and then drying;
(2') washing the carbon fiber in an HCl solution for 5-6 hours and then drying;
(3') subjecting the carbon fiber to oxidation treatment in air, followed by extraction with ethanol to obtain an activated carbon fiber.
Preferably, the concentration of the NaOH solution in step (1') is 3-6M, such as 3M, 3.1M, 3.2M, 3.3M, 3.4M, 3.5M, 3.6M, 3.7M, 3.8M, 3.9M, 4M, 4.1M, 4.2M, 4.3M, 4.4M, 4.5M, 4.6M, 4.7M, 4.8M, 4.9M, 5M, 5.1M, 5.2M, 5.3M, 5.4M, 5.5M, 5.6M, 5.7M, 5.8M, 5.9M or 6M, preferably 5M.
Preferably, the washing time in step (1') is 3-5h, for example, 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5h, preferably 4 h.
Preferably, the washing temperature in step (1') is 90-120 ℃, for example, can be 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃ or 120 ℃, preferably 100 ℃.
Preferably, the concentration of the HCl solution in step (2') is 3-6M, and may be, for example, 3M, 3.2M, 3.5M, 3.8M, 4M, 4.2M, 4.5M, 4.8M, 5M, 5.2M, 5.5M, 5.8M or 6M, preferably 5M.
Preferably, the washing time in step (2') is 5-6h, for example, 5h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h or 6h, preferably 5.5 h.
Preferably, the washing temperature in step (2') is 80-100 ℃, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ or 100 ℃, preferably 85 ℃.
Preferably, the temperature of the oxidation treatment in step (3') is 100-.
Preferably, the time of the oxidation treatment in step (3') is 3 to 5 hours, and may be, for example, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours, 4 hours, 4.1 hours, 4.2 hours, 4.3 hours, 4.4 hours, 4.5 hours, 4.6 hours, 4.7 hours, 4.8 hours, 4.9 hours or 5 hours, preferably 4 hours.
Preferably, the extraction time in step (3') is 5 to 10 hours, and may be, for example, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours, 6 hours, 6.2 hours, 6.5 hours, 6.8 hours, 7 hours, 7.2 hours, 7.5 hours, 7.8 hours, 8 hours, 8.2 hours, 8.5 hours, 8.8 hours, 9 hours, 9.2 hours, 9.5 hours, 9.8 hours or 10 hours, preferably 8 hours.
As a preferred technical scheme, the invention provides a preparation method of a carbon fiber supported noble metal catalyst, which comprises the following steps:
(1) introducing carbon-containing gas and oxygen into the gamma-alumina catalyst according to the volume ratio of (1-5):1, and reacting for 18-32h at the temperature of 500-1000 ℃ to prepare the gamma-alumina catalyst with the particle size of 10-50nm and the specific surface area of 200-1000m2Carbon fibers per gram;
(2) washing carbon fibers in a 3-6M NaOH solution for 3-5h at 90-120 ℃, then cooling to 80-100 ℃, washing the carbon fibers in a 3-6M HCl solution for 5-6h, drying, oxidizing the carbon fibers in the air for 3-5h, and then extracting for 5-10h by using ethanol to obtain activated carbon fibers;
(3) adding a stabilizer and a reducing agent into the noble metal solution, and reacting for 2-20h at 60-120 ℃ to obtain noble metal sol;
(4) soaking activated carbon fibers in the noble metal sol by adopting an isometric soaking method and/or an excess soaking method, wherein the mass ratio of the carbon fibers to the noble metal sol is 10 (1-5), adjusting the pH value to 4-5, heating and stirring at 40-80 ℃, and performing ultrasonic oscillation reaction for 5-20 h;
(5) and (3) placing the impregnated carbon fibers in inert gas, and calcining for 3-5h at the temperature of 200-400 ℃ to obtain the carbon fiber supported noble metal catalyst.
In a second aspect, the invention provides a carbon fiber-supported noble metal catalyst prepared by the preparation method of the first aspect.
In a third aspect, the invention provides a carbon fiber-supported noble metal catalyst as described in the second aspect for use in the production of a fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method of the invention adopts the mixed gas of methane, ethylene and carbon monoxide as the carbon-containing gas, the carbon fiber prepared by the method is regularly arranged in a tubular shape in a reasonable proportion range with the minimum particle size of 12nm and the maximum specific surface area of 980m2(iv) g, so that the noble metal can be uniformly dispersed in the capillary and inner surface of the carbon fiber;
(2) the carbon fiber is taken as a carbon-based carrier, the yield of the prepared carbon fiber supported noble metal catalyst is up to 99.8 percent, and the catalytic performance is preferably up to 99.5 percent;
(3) the method has the advantages of simple process, synergistic effect of each step, high yield of the prepared catalyst, excellent performance, stability and reliability.
Detailed Description
To further illustrate the technical means and effects of the present invention, the present invention is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or apparatus used are conventional products commercially available from normal sources, not indicated by the manufacturer.
Example 1 preparation of carbon fiber-supported platinum catalyst
(1) Introducing methane, ethylene, carbon monoxide and oxygen into the gamma-alumina-loaded nickel-iron alloy according to the volume ratio of 6:3:6:5, and reacting for 25 hours at 650 ℃ to obtain carbon fibers;
(2) washing carbon fibers in a 5M NaOH solution for 4 hours at 100 ℃, then cooling to 85 ℃, washing the carbon fibers in a 5M HCl solution for 5.5 hours, drying, oxidizing the carbon fibers in air at 180 ℃ for 4 hours, and then extracting with ethanol for 8 hours to obtain activated carbon fibers;
(3) adding polyethylene glycol and acetaldehyde into a platinum salt solution, and reacting for 8 hours at 100 ℃ to obtain platinum sol;
(4) soaking activated carbon fibers in the platinum sol, wherein the mass ratio of the carbon fibers to the platinum sol is 10:3, adjusting the pH value to 4-5, heating and stirring at 60 ℃, and carrying out ultrasonic oscillation reaction for 10 hours;
(5) and placing the impregnated carbon fiber in argon, and calcining for 4 hours at 300 ℃ to obtain the carbon fiber supported platinum catalyst.
Example 2 preparation of carbon fiber-supported ruthenium catalyst
(1) Introducing methane, ethylene, carbon monoxide and oxygen into the gamma-alumina-loaded nickel-iron alloy according to the volume ratio of 1:1:2:1, and reacting for 20 hours at 600 ℃ to obtain carbon fibers;
(2) washing carbon fibers in a 4M NaOH solution at 95 ℃ for 3.5h, then cooling to 82 ℃, washing the carbon fibers in a 4M HCl solution for 5.5h, drying, oxidizing the carbon fibers in air at 150 ℃ for 3.5h, and then extracting with ethanol for 9h to obtain activated carbon fibers;
(3) adding polyvinyl pyridine and hydrogen into a ruthenium salt solution, and reacting for 15h at 80 ℃ to obtain ruthenium sol;
(4) soaking activated carbon fibers in the ruthenium sol, wherein the mass ratio of the carbon fibers to the ruthenium sol is 10:4, adjusting the pH value to 4-5, heating and stirring at 50 ℃, and carrying out ultrasonic oscillation reaction for 8 hours;
(5) and placing the impregnated carbon fiber in argon, and calcining for 4.5 hours at 350 ℃ to obtain the carbon fiber supported ruthenium catalyst.
Example 3 preparation of a carbon fiber-supported Palladium catalyst
(1) Introducing methane, ethylene, carbon monoxide and oxygen into the gamma-alumina-loaded nickel-iron alloy according to the volume ratio of 2:4:4:5, and reacting for 30 hours at 800 ℃ to obtain carbon fibers;
(2) washing carbon fibers in a 5.5M NaOH solution for 4.5h at 110 ℃, then cooling to 90 ℃, washing the carbon fibers in a 5.5M HCl solution for 5.5h, drying, oxidizing the carbon fibers in air at 200 ℃ for 4.5h, and then extracting for 6h by using ethanol to obtain activated carbon fibers;
(3) adding polyvinyl alcohol and carbon monoxide into the palladium salt solution, and reacting for 5 hours at 110 ℃ to obtain palladium sol;
(4) soaking activated carbon fibers in the palladium sol, wherein the mass ratio of the carbon fibers to the palladium sol is 10:2, adjusting the pH value to 4-5, heating and stirring at 70 ℃, and carrying out ultrasonic oscillation reaction for 15 hours;
(5) and placing the impregnated carbon fiber in argon, and calcining for 3.5h at 250 ℃ to obtain the carbon fiber supported palladium catalyst.
Example 4 preparation of carbon fiber-supported rhodium catalyst
(1) Introducing methane, ethylene, carbon monoxide and oxygen into the gamma-alumina-loaded nickel according to the volume ratio of 15:5:10:6, and reacting for 18 hours at 500 ℃ to obtain carbon fibers;
(2) washing carbon fibers in a 3M NaOH solution for 3 hours at 90 ℃, then cooling to 80 ℃, washing the carbon fibers in a 3M HCl solution for 5 hours, drying, oxidizing the carbon fibers in the air at 100 ℃ for 3 hours, and then extracting with ethanol for 10 hours to obtain activated carbon fibers;
(3) adding orthosilicate ester and polyethylene glycol into the rhodium salt solution, and reacting for 20 hours at 60 ℃ to obtain rhodium sol;
(4) soaking activated carbon fibers in the rhodium sol, wherein the mass ratio of the carbon fibers to the rhodium sol is 10:1, adjusting the pH value to 4-5, heating and stirring at 40 ℃, and carrying out ultrasonic oscillation reaction for 5 hours;
(5) and (3) placing the impregnated carbon fiber in nitrogen, and calcining for 5 hours at 400 ℃ to obtain the carbon fiber supported rhodium catalyst.
Example 5 preparation of carbon fiber-supported gold catalyst
(1) Introducing methane, ethylene, carbon monoxide and oxygen into the gamma-alumina loaded iron according to the volume ratio of 3:2:2:7, and reacting for 32 hours at 1000 ℃ to obtain carbon fibers;
(2) washing carbon fibers in a 6M NaOH solution for 5 hours at 120 ℃, then cooling to 100 ℃, washing the carbon fibers in a 6M HCl solution for 6 hours, drying, oxidizing the carbon fibers in air at 220 ℃ for 5 hours, and then extracting for 5 hours by using ethanol to obtain activated carbon fibers;
(3) adding sodium citrate and polyvinylpyrrolidone into the gold salt solution, and reacting for 2h at 120 ℃ to obtain gold sol;
(4) soaking activated carbon fibers in the gold sol, wherein the mass ratio of the carbon fibers to the gold sol is 2:1, adjusting the pH value to 4-5, heating and stirring at 80 ℃, and carrying out ultrasonic oscillation reaction for 20 hours;
(5) and (3) placing the impregnated carbon fiber in helium, and calcining for 3h at 200 ℃ to obtain the carbon fiber supported gold catalyst.
Comparative example 1
The volume ratio of methane, ethylene, carbon monoxide and oxygen was 4:3:2:3 compared to example 1, and other preparation conditions were the same as in example 1.
Comparative example 2
Compared with the embodiment 1, the volume ratio of the methane, the ethylene, the carbon monoxide and the oxygen is 1:1:4:2, and other preparation conditions are the same as the embodiment 1.
Comparative example 3
Compared with the embodiment 1, the carbon-containing gas only contains methane, the volume ratio of the methane to the oxygen is 3:1, and other preparation conditions are the same as the embodiment 1.
Comparative example 4
Compared with the embodiment 1, the carbon-containing gas only contains ethylene, the volume ratio of the ethylene to the oxygen is 3:1, and other preparation conditions are the same as the embodiment 1.
Comparative example 5
Compared with the embodiment 1, the carbon-containing gas only contains carbon monoxide, the volume ratio of the carbon monoxide to the oxygen is 3:1, and other preparation conditions are the same as the embodiment 1.
Comparative example 6
Compared with example 1, activated carbon is used as the carbon-based support, and the other preparation processes are the same as example 1.
Comparative example 7
The mass ratio of carbon fiber to platinum sol was 20:1 as compared with example 1, and other preparation conditions were the same as in example 1.
Comparative example 8
The mass ratio of carbon fiber to platinum sol was 5:4 as compared with example 1, and other preparation conditions were the same as in example 1.
Characterization of carbon fiber supported noble metal catalyst
The carbon-based supported noble metal catalysts prepared in examples 1-5 and comparative examples 1-8 were characterized using a scanning electron microscope and a pore size analyzer, and the results are shown in table 1.
TABLE 1 characterization of carbon-based supported noble metal catalysts
From comparison of examples 1 to 5, when the volume ratio of methane, ethylene, carbon monoxide and oxygen is 1:1:2:1, the carbon fibers are produced in a tubular regular arrangement with a particle size of 12nm at the minimum and a specific surface area of 980m at the maximum2The catalyst can be used as an excellent carbon-based carrier to load noble metal, has good dispersion performance, and uniformly distributes the noble metal.
Compared with the embodiment 1, the volume ratio of methane, ethylene, carbon monoxide and oxygen in the comparative examples 1-2 is unreasonable, and the prepared carbon fiber has irregular shape, larger particle size, reduced specific surface area and poorer dispersion on noble metals; comparative examples 3 to 5 use carbon-containing gas with a single component, the prepared carbon fiber has an irregular shape, the particle size reaches micron level, the specific surface area is significantly reduced, and the noble metal cannot be uniformly dispersed in the carbon fiber and is only concentrated on a certain part of the carbon fiber; comparative example 6 using activated carbon as a carbon base, the specific surface area of activated carbon is small, and noble metal cannot be uniformly dispersed in activated carbon; the mass ratio of the carbon fibers of comparative examples 7 to 8 to the noble metal sol was not reasonable, and the noble metal was not uniformly distributed although the prepared carbon fibers had a small particle size, a large specific surface area, and a regular structure.
Yield and catalytic performance of carbon-based noble metal-supported catalyst
The yields and catalytic properties of the carbon-based supported noble metal catalysts prepared in examples 1-5 and comparative examples 1-8 are shown in table 2.
TABLE 2 yield and catalytic performance of carbon-based supported noble metal catalysts
| Numbering | Yield (%) | Catalytic Properties (%) |
| Example 1 | 99.8 | 99.5 |
| Example 2 | 99.2 | 98.8 |
| Example 3 | 98.6 | 98.1 |
| Example 4 | 97.8 | 97.9 |
| Example 5 | 97.5 | 97.3 |
| Comparative example 1 | 76.3 | 34.1 |
| Comparative example 2 | 77.4 | 35.2 |
| Comparative example 3 | 43.5 | 26.7 |
| Comparative example 4 | 46.7 | 29.4 |
| Comparative example 5 | 45.2 | 27.4 |
| Comparative example 6 | 65.3 | 28.2 |
| Comparative example 7 | 99.2 | 47.9 |
| Comparative example 8 | 98.9 | 50.1 |
The yield of the carbon fiber supported noble metal catalyst prepared by the embodiment of the invention is higher than 97%, and the catalytic performance is higher than 97%; compared with the comparative examples 1 to 5, the yield of the carbon fiber supported noble metal catalyst is obviously reduced and the catalytic performance is obviously reduced due to unreasonable types and volumes of carbon-containing gases; the comparative example 6 uses the activated carbon as the carbon base, has large particle size, small specific surface area and poor dispersion performance, and influences the catalytic performance of the noble metal; the carbon fibers prepared in the comparative examples 7 to 8 have small particle size, large specific surface area and regular structure, but the noble metal is not uniformly distributed, so that the catalytic performance of the catalyst is obviously reduced.
In summary, according to the preparation method of the carbon fiber supported noble metal catalyst, the mixed gas of methane, ethylene and carbon monoxide is used as the carbon-containing gas and is in a reasonable proportion range with oxygen, the prepared carbon fiber has a regular structure, a small particle size, a large specific surface area and good dispersion performance, and the carbon fiber supported noble metal catalyst prepared by using the carbon fiber as a carbon base has high yield and excellent catalytic performance.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (49)
1. A preparation method of a carbon fiber supported noble metal catalyst is characterized by comprising the following steps:
(1) introducing carbon-containing gas and oxygen into the gamma-alumina supported nickel-iron alloy catalyst, and reacting for 18-32h at the temperature of 500-1000 ℃ to prepare the gamma-alumina supported nickel-iron alloy catalyst with the particle size of 10-50nm and the specific surface area of 200-1000m2Carbon fibers per gram;
(2) adding a stabilizer and a reducing agent into the noble metal solution, and reacting for 2-20h at 60-120 ℃ to obtain noble metal sol;
(3) soaking carbon fibers in the noble metal sol by adopting an isometric soaking method and/or an excess soaking method, wherein the mass ratio of the carbon fibers to the noble metal sol is 10 (1-5), adjusting the pH value to 4-5, heating and stirring, and carrying out ultrasonic oscillation reaction for 5-20 h;
(4) placing the impregnated carbon fibers in inert gas for calcining to obtain the carbon fiber supported noble metal catalyst;
the carbon-containing gas is a combination of methane, ethylene and carbon monoxide;
the volume ratio of the methane to the ethylene to the carbon monoxide is (1-3) to (1-2) to 2;
the volume ratio of the carbon-containing gas to the oxygen is (1-5): 1.
2. The method according to claim 1, wherein the volume ratio of the carbon-containing gas to the oxygen gas in step (1) is 3: 1.
3. The method according to claim 1, wherein the volume ratio of methane, ethylene and carbon monoxide is 2:1: 2.
4. The method as claimed in claim 1, wherein the temperature of the reaction in step (1) is 500-800 ℃.
5. The method according to claim 4, wherein the temperature of the reaction in the step (1) is 650 ℃.
6. The method according to claim 1, wherein the reaction time in step (1) is 20 to 30 hours.
7. The method according to claim 6, wherein the reaction time in step (1) is 25 hours.
8. The method according to claim 1, wherein the noble metal of step (2) comprises any one of platinum, ruthenium, palladium, rhodium, iridium, or gold, or a combination of at least two thereof.
9. The method according to claim 8, wherein the noble metal in the step (2) is platinum.
10. The method according to claim 1, wherein the stabilizer in step (2) comprises any one of polyethylene glycol, polyvinyl pyridine, polyvinyl alcohol, orthosilicate ester or sodium citrate or a combination of at least two thereof.
11. The method according to claim 10, wherein the stabilizer in step (2) is polyethylene glycol.
12. The method according to claim 1, wherein the reducing agent in step (2) comprises any one of hydrogen, acetaldehyde, carbon monoxide, polyethylene glycol or polyvinylpyrrolidone or a combination of at least two thereof.
13. The method according to claim 12, wherein the reducing agent in the step (2) is acetaldehyde.
14. The method according to claim 1, wherein the temperature of the reaction in the step (2) is 80 to 110 ℃.
15. The method according to claim 14, wherein the temperature of the reaction in the step (2) is 100 ℃.
16. The method according to claim 1, wherein the reaction time in step (2) is 5 to 15 hours.
17. The method according to claim 16, wherein the reaction time in the step (2) is 8 hours.
18. The production method according to claim 1, wherein the mass ratio of the carbon fibers to the noble metal sol in step (3) is 10 (3-4).
19. The method according to claim 1, wherein the heating temperature in the step (3) is 40 to 80 ℃.
20. The method according to claim 19, wherein the heating temperature in the step (3) is 60 ℃.
21. The method according to claim 1, wherein the reaction time in step (3) is 8 to 15 hours.
22. The method according to claim 21, wherein the reaction time in the step (3) is 10 hours.
23. The method according to claim 1, wherein the inert gas in step (4) comprises any one of nitrogen, helium or argon or a combination of at least two thereof.
24. The method according to claim 23, wherein the inert gas in the step (4) is argon gas.
25. The method as claimed in claim 1, wherein the temperature of the calcination in the step (4) is 200-400 ℃.
26. The method of claim 25, wherein the temperature of the calcining in step (4) is 300 ℃.
27. The method of claim 1, wherein the calcination time in step (4) is 3-5 h.
28. The method of claim 27, wherein the calcination in step (4) is carried out for 4 hours.
29. The method of claim 1, further comprising a step of purifying and activating the carbon fiber after the step (1).
30. The method for preparing according to claim 29, wherein the purifying and activating carbon fiber comprises:
(1') washing the carbon fiber in NaOH solution for 3-5h, and then drying;
(2') washing the carbon fiber in an HCl solution for 5-6 hours and then drying;
(3') subjecting the carbon fiber to oxidation treatment in air, followed by extraction with ethanol to obtain an activated carbon fiber.
31. The method of claim 30, wherein the concentration of the NaOH solution in step (1') is 3-6M.
32. The method of claim 31, wherein the NaOH solution of step (1') has a concentration of 5M.
33. The method according to claim 30, wherein the washing in step (1') is carried out for 4 hours.
34. The method according to claim 30, wherein the washing temperature in the step (1') is 90 to 120 ℃.
35. The method according to claim 34, wherein the washing temperature in the step (1') is 100 ℃.
36. The method of claim 30, wherein the concentration of the HCl solution in step (2') is 3-6M.
37. The method of claim 36, wherein the HCl solution of step (2') has a concentration of 5M.
38. The method of claim 30, wherein the washing in step (2') is carried out for 5.5 hours.
39. The method according to claim 30, wherein the washing temperature in the step (2') is 80 to 100 ℃.
40. The method according to claim 39, wherein the washing temperature in the step (2') is 85 ℃.
41. The method as claimed in claim 30, wherein the temperature of the oxidation treatment in the step (3') is 100-220 ℃.
42. The production method according to claim 41, wherein the temperature of the oxidation treatment in the step (3') is 180 ℃.
43. The method according to claim 30, wherein the time for the oxidation treatment in the step (3') is 3 to 5 hours.
44. The method according to claim 43, wherein the time for the oxidation treatment in the step (3') is 4 hours.
45. The method of claim 30, wherein the extraction time in step (3') is 5-10 hours.
46. The method of claim 45, wherein the extraction time of step (3') is 8 hours.
47. The method of claim 1, comprising the steps of:
(1) to gamma-alumina catalystIntroducing carbon-containing gas and oxygen into the reagent according to the volume ratio of (1-5):1, and reacting for 18-32h at the temperature of 500-2Carbon fibers per gram;
(2) washing carbon fibers in a 3-6M NaOH solution for 3-5h at 90-120 ℃, then cooling to 80-100 ℃, washing the carbon fibers in a 3-6M HCl solution for 5-6h, drying, oxidizing the carbon fibers in the air for 3-5h, and then extracting for 5-10h by using ethanol to obtain activated carbon fibers;
(3) adding a stabilizer and a reducing agent into the noble metal solution, and reacting for 2-20h at 60-120 ℃ to obtain noble metal sol;
(4) soaking activated carbon fibers in the noble metal sol by adopting an isometric soaking method and/or an excess soaking method, wherein the mass ratio of the carbon fibers to the noble metal sol is 10 (1-5), adjusting the pH value to 4-5, heating and stirring at 40-80 ℃, and performing ultrasonic oscillation reaction for 5-20 h;
(5) and (3) placing the impregnated carbon fibers in inert gas, and calcining for 3-5h at the temperature of 200-400 ℃ to obtain the carbon fiber supported noble metal catalyst.
48. A carbon fiber-supported noble metal catalyst produced by the production method as set forth in any one of claims 1 to 47.
49. A noble metal-on-carbon fiber catalyst according to claim 48 for use in the production of a fuel cell.
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