CN113571720B - Carbon-based catalyst containing metal platinum, preparation method and application thereof - Google Patents
Carbon-based catalyst containing metal platinum, preparation method and application thereof Download PDFInfo
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- CN113571720B CN113571720B CN202110846392.3A CN202110846392A CN113571720B CN 113571720 B CN113571720 B CN 113571720B CN 202110846392 A CN202110846392 A CN 202110846392A CN 113571720 B CN113571720 B CN 113571720B
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 48
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 5
- 229940039790 sodium oxalate Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 18
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 15
- 239000004917 carbon fiber Substances 0.000 abstract description 15
- 238000000967 suction filtration Methods 0.000 abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 abstract description 9
- 239000008139 complexing agent Substances 0.000 abstract description 9
- 239000011261 inert gas Substances 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 238000011282 treatment Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003057 platinum Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 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 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
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
- H01M4/925—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
-
- 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
-
- 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 discloses a carbon-based catalyst containing metal platinum, a preparation method and application thereof, and belongs to the technical field of catalysts. Which comprises the following steps: adding a solution containing a metal platinum precursor and pretreated carbon fibers into a mixed alcohol reducing agent, adding a complexing agent, heating and reducing under inert gas atmosphere, and obtaining the carbon-based catalyst containing metal platinum through centrifugal suction filtration, washing and drying. The preparation method of the carbon-based catalyst containing the metal platinum has the advantages of simple and efficient synthesis process, easy amplification, capability of effectively carrying out mass production to obtain the high-quality carbon-based catalyst, suitability for various Pt loading amounts and stronger practicability.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a carbon-based catalyst containing metal platinum, a preparation method and application thereof.
Background
With the increasing exhaustion of petrochemical energy sources and the increasing increase of environmental pollution, the development and utilization of new energy sources become an emerging hot spot industry at present. In recent years, efforts have been made to explore utilization modes which have both zero emission and higher energy utilization. Among the various energy utilization modes, fuel cells are becoming increasingly popular because they have the advantages of less environmental pollution, no limitation to carnot cycle, and the like. Catalysts play a vital role in the conversion of hydrogen and oxygen chemical energy into electrical energy. The most widely used platinum-based catalysts in the market today.
At present, a large number of synthesis methods of platinum-based catalysts, such as an impregnation method, a high-temperature roasting method, a vacuum sputtering method, an ion exchange method, an electrochemical deposition method, a sol-gel method, a gas-liquid phase reduction method, a glow discharge plasma method, a displacement method, a microwave-promoted reduction method and the like, are reported in the literature, and all the processes have respective advantages and disadvantages, but engineering amplification has certain problems, and meanwhile, due to the existence of technical barriers, the expensive technology in the foreign Zhuang Xinmo Fenghe field is in strict confidentiality, and no literature about the technology for amplifying and preparing the platinum-based catalysts has been reported. The enlarged preparation and mass production of high-consistency, high-batch-stability catalysts are important points and difficulties in the synthesis technology of platinum-based catalysts. Meanwhile, the synthesis process needs to be considered.
CN100488633C discloses a carbon-supported platinum-based catalyst for fuel cells and a preparation method thereof, wherein a reducing agent adopts a mixed solution of ethylene glycol, glycerol and 1-3 propylene glycol, an organic solvent is a mixed solution of acetone and one or two of the ethylene glycol and the glycerol, chloroplatinic acid is reduced into platinum colloid through the mixed solution, then a carbon material is added, stirring is carried out for 24-48 hours, and HCl and H are adopted 2 OSO 4 Or HNO (HNO) 3 The pH value of the aqueous solution is regulated to be 1-4, and the Pt-based catalyst is obtained through ultrasonic treatment, vibration and filtration, but the whole process flow of the process is longer, the process adopts a process of firstly reducing and then loading, and the acting force of the platinum-based nano particles and carbon is weaker.
CN10458801a discloses a synthesis process and method for synthesizing Pt/C catalyst by combining microwave method and polyol method, which comprises heating carbon black with hydrogen peroxide and isopropanol solution, mixing and dispersing carbon black, chloroplatinic acid, deionized water and reducing polyol, heating with microwave, and spray drying to obtain catalyst with high activity. However, this method has the disadvantage that the microwave synthesis method is not yet mature in terms of industrial scale-up and further investigation is required.
Patent CN102218331a describes a preparation method of carbon-based Pt nanomaterial, which is to heat-treat activated carbon in concentrated sulfuric acid and concentrated nitric acid, and then reduce the activated carbon by ethylene glycol to obtain a PtC nano catalyst, but the ORR linear scanning curve of the catalyst obtained by this method shows that the limiting diffusion current density of the catalyst does not reach the theoretical value, and the stability is not examined, which illustrates the limitation of the synthesis method.
The patent CN106129424B discloses a high-efficiency and batch-method fuel cell catalyst production method, which comprises the steps of fully dispersing organic weak acid and a carbon carrier by ultrasonic, heating at 200-400 ℃ for 20-40min, adding the carbon carrier into ethylene glycol solution containing chloroplatinic acid, regulating pH to 9-11 by using NaOH solution of ethylene glycol, and heating to 100-120 ℃ by a batch microwave method to obtain the Pt/C catalyst.
CN110252290A describes a preparation method of a Pt/C nano material, which comprises the steps of dispersing glycol solution of Pt and carbon powder in the glycol and cyclohexanone solution, carrying out ultrasonic dispersion for 1-3h, and then reducing by a microwave method to obtain the Pt/C catalyst. However, such a process has a disadvantage in that the microwave method is not suitable for industrial production, thus preventing the application of magnification.
Disclosure of Invention
The invention aims to provide a carbon-based catalyst containing metal platinum, a preparation method and application thereof, so as to solve the problem that the existing synthesis method of the platinum-carbon catalyst is difficult to produce in a large scale due to the limitation; the obtained platinum-carbon catalyst has poor structural dispersity and has the problem of poor electrochemical reaction stability in practical application.
The technical scheme for solving the technical problems is as follows:
a method for preparing a carbon-based catalyst containing metal platinum, comprising the steps of:
adding a solution containing a metal platinum precursor and pretreated carbon fibers into a mixed alcohol reducing agent, adding a complexing agent, heating and reducing under inert gas atmosphere, and obtaining the carbon-based catalyst containing metal platinum through centrifugal suction filtration, washing and drying.
Further, in a preferred embodiment of the present invention, the preparation method of the carbon-based catalyst containing metal platinum includes the following steps:
(1) Adding a solution containing a metal platinum precursor, pretreated carbon fibers and a complexing agent into a mixed alcohol reducer, and performing ultrasonic dispersion to obtain a suspension;
in the mixed solution, the concentration of the metal platinum-containing precursor is 1g/L to 15g/L; the mass ratio of the metal-containing platinum precursor to the pretreated carbon fiber is 1: (1/2-7); the mass ratio of the metal-containing platinum precursor to the complexing agent is 1: (1/7-7);
(2) After regulating the pH of the suspension to 8-14, heating and reducing for 4-12 hours in inert gas atmosphere to obtain a reaction solution;
(3) Adjusting the pH of the reaction solution to 1-4, carrying out ultrasonic oscillation, and stirring at room temperature for 8-15 h to obtain a treatment solution;
(4) And (3) carrying out centrifugal suction filtration, washing and drying on the treatment solution to obtain the carbon-based catalyst containing the metal platinum.
Further, in a preferred embodiment of the present invention, the solution of the metal-containing platinum precursor is prepared by dissolving the metal-containing platinum precursor in an alcohol solution, and the concentration is 20g/L to 100g/L;
the metal-containing platinum precursor comprises: chloroplatinic acid or platinum salt; the platinum salt includes: potassium or sodium chloroplatinate;
the alcohol solution comprises ethylene glycol or glycerol.
Further, in a preferred embodiment of the present invention, the pretreatment step of pretreating the carbon fiber includes:
firstly, soaking carbon fiber in pure acetone solution for 5-12 h, after suction filtration and drying, soaking in 15-20wt% hydrogen peroxide solution for 5-12 h, after suction filtration and drying, soaking in 10-30wt% nitric acid aqueous solution for 5-12 h, after suction filtration and drying, roasting at high temperature of 300-600 ℃ for 2-5 h under the protection of inert gas, thus obtaining pretreated carbon fiber.
Further, in a preferred embodiment of the present invention, the carbon fiber includes at least one of conductive carbon black, graphene oxide, graphitic carbon, carbon nanotube, carbon nanofiber and coconut shell carbon.
Further, in a preferred embodiment of the present invention, the above-mentioned mixed alcohol reducing agent includes: ethylene glycol and glycerol in a volume ratio of 1: (1/5-5).
Further, in a preferred embodiment of the present invention, the complexing agent is one or more of sodium citrate, sodium oxalate, sodium ethylenediamine tetraacetate, and sodium tartrate.
Further, in a preferred embodiment of the present invention, the above-mentioned heat reduction treatment conditions are: the reaction temperature is 120-180 ℃, and the oil bath is used for heating for 2-5 h.
The carbon-based catalyst containing metal platinum prepared by the preparation method of the carbon-based catalyst containing metal platinum.
The application of the carbon-based catalyst containing the metal platinum in proton exchange membrane fuel cell materials.
The invention has the following beneficial effects:
1. the catalyst synthesized by the method has highly uniform cluster particles and very good crystallinity of the particles, which is shown by a spherical aberration scanning projection microscope. The prepared Pt nano material has very good structural dispersity and excellent stability of electrochemical reaction. Meanwhile, the preparation process is easy to amplify.
2. The preparation method of the carbon-based catalyst containing the metal platinum has the advantages of simple and efficient synthesis process, easy amplification, capability of effectively carrying out mass production to obtain the high-quality carbon-based catalyst, suitability for various Pt loading amounts and stronger practicability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a TEM photograph of a carbon-based catalyst containing metal platinum of example 1 of the present invention;
FIG. 2 is a TEM photograph of a metal-platinum-containing carbon-based catalyst of comparative example 1 of the present invention;
FIG. 3 is a projection view of a spherical aberration scan of a carbon-based catalyst containing platinum according to example 1 of the present invention;
FIG. 4 is an ORR curve for the metal platinum-containing carbon-based catalysts of example 1 and comparative example 1 of the present invention.
Detailed Description
The principles and features of the present invention are described below with reference to the following examples and drawings, which are provided for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Aiming at the limitations existing in the existing synthesis method of the platinum-carbon catalyst, the large-scale production of the platinum-carbon catalyst is difficult; the obtained platinum-carbon catalyst has poor structural dispersity and poor electrochemical reaction stability in practical application, and the invention provides a preparation method of a carbon-based catalyst containing metal platinum, which comprises the following steps:
adding a solution containing a metal platinum precursor and pretreated carbon fibers into a mixed alcohol reducing agent, adding a complexing agent, heating and reducing under inert gas atmosphere, and obtaining the carbon-based catalyst containing metal platinum through centrifugal suction filtration and washing.
Specifically, the preparation method of the carbon-based catalyst containing the metal platinum comprises the following steps:
(1) Adding the solution containing the metal platinum precursor, the pretreated carbon fiber and the complexing agent into a mixed alcohol reducer, and performing ultrasonic dispersion to obtain a suspension.
In the mixed solution, the concentration of the metal platinum-containing precursor is 1g/L to 15g/L; the mass ratio of the metal-containing platinum precursor to the pretreated carbon fiber is 1: (1/2-7); the mass ratio of the metal-containing platinum precursor to the complexing agent is 1: (1/7-7).
Wherein the solution containing the metal platinum precursor is prepared by dissolving the metal platinum precursor in an alcohol solution, and the concentration is 20g/L-100g/L; the metal-containing platinum precursor comprises: chloroplatinic acid or platinum salt; the platinum salt includes: potassium or sodium chloroplatinate; the alcohol solution comprises ethylene glycol or glycerol.
The pretreatment step of pretreating the carbon fiber comprises the following steps: firstly, soaking carbon fiber in pure acetone solution for 5-12 h, after suction filtration and drying, soaking in 15-20wt% hydrogen peroxide solution for 5-12 h, after suction filtration and drying, soaking in 10-30wt% nitric acid aqueous solution for 5-12 h, after suction filtration and drying, roasting at high temperature of 300-600 ℃ for 2-5 h under the protection of inert gas, thus obtaining pretreated carbon fiber. The carbon fiber adopted by the invention comprises at least one of conductive carbon black, graphene oxide, graphite carbon, carbon nano-tube, carbon nano-fiber and coconut shell carbon. Wherein the conductive carbon black: vulcan XC72, ketjen EC600J, blackpearls 3000, etc.
The complexing agent is one or more of sodium citrate, sodium oxalate, sodium ethylenediamine tetraacetate and sodium tartrate.
The mixed alcohol reducing agent comprises: ethylene glycol and glycerol in a volume ratio of 1: (1/5-5).
(2) After regulating the pH of the suspension to 8-14, heating and reducing for 4-12 hours in inert gas atmosphere to obtain a reaction solution;
the treatment conditions of the heating reduction are as follows: the reaction temperature is 120-180 ℃, and the oil bath is used for heating for 2-5 h.
In this step, the water vapor generated by the oil bath heating can be returned to the heating system by means of condensation reflux or heated by a high-pressure reaction kettle.
The alkaline solution for adjusting the pH value of the suspension comprises the following components: aqueous ammonia or aqueous solutions of sodium oxalate, potassium carbonate, sodium bicarbonate, sodium hydroxide, etc.
(3) Adjusting the pH value of the reaction solution to 1-4, carrying out ultrasonic oscillation, and stirring at room temperature for 8-15 h to obtain a treatment solution.
In this step, HCl/H at a concentration of 5wt% was used 2 O adjusts the pH value of the reaction solution.
(4) And (3) carrying out centrifugal suction filtration, washing and drying on the treatment solution to obtain the carbon-based catalyst containing the metal platinum. In the step, a mobile phase filter or a high-speed centrifuge is used for separating solid from liquid of a treatment solution, washing is carried out, when a metal-containing platinum precursor is platinum salt, washing is carried out until no chloride ions exist in filtrate, and the obtained filter cake is subjected to vacuum drying or freeze drying, so that the catalyst is obtained.
Example 1:
the preparation method of the carbon-based catalyst containing metal platinum of the embodiment comprises the following steps:
soaking Katjen carbon black in pure acetone for 8 hours, performing suction filtration and drying, then performing hydrogen peroxide treatment by 20wt.% for 12 hours, performing suction filtration and drying, performing treatment in a 30wt.% nitric acid aqueous solution for 12 hours, and finally performing high-temperature roasting in a nitrogen environment at 300 ℃; dispersing 0.3g of the carbon carrier in 400mL of glycol/glycerol solution (volume ratio: glycol: glycerol=1), preparing 100g/L of ethylene glycol solution of chloroplatinic acid, taking 18.6mL of the chloroplatinic acid/ethylene glycol solution, adding the solution into the ethylene glycol solution containing the carbon carrier, fully stirring and mixing, taking 1.86g of sodium oxalate, adding the solution into the solution, performing ultrasonic dispersion to form suspension, adding the ethylene glycol solution of NaOH (5.wt%), and adjusting pH=13 of the system; heating the suspension to 120 ℃ under the protection of nitrogen, and maintaining the reaction time for 10 hours; after the completion, the pH of the solution was adjusted to 1-4, stirred at room temperature for 10 hours, and the mixture after the reaction was filtered, washed until no chlorine ions were present, and dried.
The metal platinum-containing carbon-based catalyst of this example was pulverized to obtain 1g of the metal platinum-containing carbon-based catalyst having a platinum loading of 70%, expressed as Pt/C-70%.
Example 2
According to the preparation method of example 1, the ketjen carrier was subjected to a series of treatments at 400 ℃, 500 ℃ and 600 ℃ respectively, and the remaining preparation conditions were unchanged, to obtain a metal platinum-containing carbon-based catalyst having a platinum loading of 70%.
Example 3
According to the preparation method of example 1, the added alkali solution is potassium carbonate, sodium bicarbonate, sodium hydroxide and ammonia water respectively to adjust the pH of the dispersed phase to 13, and the rest of the preparation conditions are unchanged, so as to obtain the carbon-based catalyst containing metal platinum with 70% of platinum loading.
Example 4
According to the preparation method of example 1, the pH of the dispersed phase was adjusted to 8, 9, 10, 11 and 12, respectively, by adding sodium carbonate solution, and the remaining preparation conditions were unchanged, to obtain a metal platinum-containing carbon-based catalyst having a platinum loading of 70%.
Example 5
According to the preparation method of example 1, the reduction temperatures are respectively: 140 ℃, 160 ℃ and 180 ℃. The rest preparation conditions are unchanged, and the carbon-based catalyst containing the metal platinum with the platinum loading of 70% is obtained.
Example 6
According to the preparation method of example 1, the ratio of ethylene glycol to glycerol added is 1: 2. 1: 1. 2:1, the total amount is kept unchanged, and the rest of the preparation conditions are unchanged, so that the carbon-based catalyst containing the metal platinum with the platinum loading of 70% is obtained.
Comparative example 1
The synthesis procedure and method employed was essentially the same as in example 1, except that the alcohol reducing agent was a pure ethylene glycol solution, and the remaining conditions and procedures were identical.
Test example 1
The results of transmission electron microscope scanning of the metal-platinum-containing carbon-based catalysts obtained in example 1 and comparative example 1 are shown in fig. 1 and 2.
Test example 2
The results of the spherical aberration scanning projection microscope on the platinum-containing carbon-based catalyst obtained in example 1 are shown in fig. 3.
From an analysis of FIGS. 1 to 3, it can be seen that the metal-platinum-containing carbon-based catalyst of the present invention has highly uniform cluster particles and is excellent in particle crystallinity as compared with the carbon-based catalyst of the comparative example.
Test example 3
The performance of the metal platinum-containing carbon-based catalysts obtained in example 1 and comparative example 1 was tested, and the data are shown in the following table and fig. 4:
from the above table and the figures, it can be seen that the carbon-based catalyst of the present invention has better catalytic performance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (3)
1. A method for preparing a carbon-based catalyst containing metal platinum, comprising the steps of:
soaking Katjen carbon black in pure acetone for 8h, filtering and drying, then treating with 20wt% hydrogen peroxide for 12 hours, filtering and drying, then treating in 30wt% nitric acid aqueous solution for 12 hours, and finally roasting at high temperature under nitrogen environment and 300 ℃ to obtain a carbon carrier;
dispersing 0.3. 0.3g of the carbon carrier in a 400mL ethylene glycol/glycerol solution, wherein the volume ratio of the ethylene glycol to the glycerol is 1; preparing 100g/L of ethylene glycol solution of chloroplatinic acid, adding 18.6ml of ethylene glycol solution of chloroplatinic acid into ethylene glycol/glycerol solution containing a carbon carrier, fully stirring and mixing, adding 1.86g of sodium oxalate into the solution, performing ultrasonic dispersion to form a suspension, adding 5wt% of ethylene glycol solution of NaOH, and regulating the pH of a system to be 13; heating the suspension to 120 ℃ under the protection of nitrogen, and maintaining the reaction time to be 10h; after the completion, the pH of the solution is regulated to be 1-4, the solution is stirred for 10 hours at room temperature, the mixture after the reaction is filtered, washed until no chloride ions exist, and then dried;
the metal platinum-containing carbon-based catalyst, after grinding, yielded a metal platinum-containing carbon-based catalyst with a platinum loading of 70% of 1g, expressed as Pt/C-70%.
2. The metal-platinum-containing carbon-based catalyst produced by the method for producing a metal-platinum-containing carbon-based catalyst according to claim 1.
3. Use of a carbon-based catalyst comprising metal platinum as claimed in claim 2 in proton exchange membrane fuel cell materials.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428882A (en) * | 2001-12-25 | 2003-07-09 | 中国科学院大连化学物理研究所 | Preparation method of proton-exchange membrane fuel cell electrode catalyst |
| CN1803292A (en) * | 2005-12-19 | 2006-07-19 | 华南理工大学 | Carbon-carried platinum-based catalyst for fuel cell and its preparation method |
| CN1994563A (en) * | 2006-11-21 | 2007-07-11 | 华南理工大学 | Carbon supported noble metal catalyst and method for preparing same |
| CN102327771A (en) * | 2011-07-14 | 2012-01-25 | 华南理工大学 | Method for preparing carbon-loaded platinum-based electro-catalyst by microwave organosol method |
| CN102773095A (en) * | 2012-08-03 | 2012-11-14 | 上海锦众信息科技有限公司 | Method for preparing platinum-based catalyst for fuel cell |
| CN108232207A (en) * | 2016-12-14 | 2018-06-29 | 北京有色金属研究总院 | A kind of preparation method of nm Pt catalyst |
| CN108963282A (en) * | 2018-07-05 | 2018-12-07 | 中山大学 | A kind of fuel cell carbon carried platinum-based catalyst and the preparation method and application thereof of solvent-thermal method reduction |
| CN110112430A (en) * | 2019-04-19 | 2019-08-09 | 贵研铂业股份有限公司 | A kind of platinum alloy carbon-supported powder and preparation method thereof |
| CN111106357A (en) * | 2019-12-16 | 2020-05-05 | 江苏大学 | Preparation method and application of platinum-based catalyst based on etching treatment of carbon carrier |
| CN112823880A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Catalyst with high metal loading capacity and preparation and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210008535A1 (en) * | 2020-07-29 | 2021-01-14 | HyPoint Inc. | Method for producing catalysts with nanoparticles of platinum and its alloys with metals |
-
2021
- 2021-07-26 CN CN202110846392.3A patent/CN113571720B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428882A (en) * | 2001-12-25 | 2003-07-09 | 中国科学院大连化学物理研究所 | Preparation method of proton-exchange membrane fuel cell electrode catalyst |
| CN1803292A (en) * | 2005-12-19 | 2006-07-19 | 华南理工大学 | Carbon-carried platinum-based catalyst for fuel cell and its preparation method |
| CN1994563A (en) * | 2006-11-21 | 2007-07-11 | 华南理工大学 | Carbon supported noble metal catalyst and method for preparing same |
| CN102327771A (en) * | 2011-07-14 | 2012-01-25 | 华南理工大学 | Method for preparing carbon-loaded platinum-based electro-catalyst by microwave organosol method |
| CN102773095A (en) * | 2012-08-03 | 2012-11-14 | 上海锦众信息科技有限公司 | Method for preparing platinum-based catalyst for fuel cell |
| CN108232207A (en) * | 2016-12-14 | 2018-06-29 | 北京有色金属研究总院 | A kind of preparation method of nm Pt catalyst |
| CN108963282A (en) * | 2018-07-05 | 2018-12-07 | 中山大学 | A kind of fuel cell carbon carried platinum-based catalyst and the preparation method and application thereof of solvent-thermal method reduction |
| CN110112430A (en) * | 2019-04-19 | 2019-08-09 | 贵研铂业股份有限公司 | A kind of platinum alloy carbon-supported powder and preparation method thereof |
| CN112823880A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Catalyst with high metal loading capacity and preparation and application thereof |
| CN111106357A (en) * | 2019-12-16 | 2020-05-05 | 江苏大学 | Preparation method and application of platinum-based catalyst based on etching treatment of carbon carrier |
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