CN116914168A - Sandwich-structure mixed carbon carrier-supported platinum particle electrocatalyst and preparation method thereof - Google Patents
Sandwich-structure mixed carbon carrier-supported platinum particle electrocatalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
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- 239000003054 catalyst Substances 0.000 abstract description 63
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/90—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
-
- 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 sandwich structure mixed carrier supported low-platinum electrocatalyst and a preparation method thereof, graphene oxide is obtained through stripping of carbon nanotubes, the graphene oxide is connected with the carbon nanotubes together due to the action of chemical bonds to form a carbon composite material with a carbon nanotube-connected graphene oxide structure, the material has more excellent specific surface area than a single carbon nanotube, and in order to prevent partial stacking in the material reduction process, carbon black is embedded into the carbon nanotube-connected graphene material after surface functionalization treatment, so that the sandwich structure mixed carrier is formed. The carbon black material is used for inhibiting the stacking of graphene, so that the specific surface area of the composite material and the exposure of noble metal attachment sites are further improved, platinum nano particles with fine particles and uniform dispersion can be obtained, and a large number of pores are formed in the sandwich structure mixed carrier, so that convenience is brought to the mass transfer of the catalyst in the electrolyte in the subsequent electrochemical process, the reduction rate of oxygen is accelerated, and the activity of the catalyst is improved. The prepared platinum mixed carrier catalyst shows good electrochemical active area and excellent oxygen reduction performance.
Description
Technical Field
The invention belongs to the technical field of platinum-carbon catalyst preparation, and particularly relates to a preparation method of a sandwich structure mixed carrier supported low-platinum electrocatalyst.
Background
Currently, the energy crisis and pollution problems caused by the rapid consumption of fossil energy are increasingly aggravated. Proton Exchange Membrane Fuel Cells (PEMFCs) are low-temperature, efficient energy conversion devices that convert hydrogen energy into electrical energy, green hydrogen is oxidized into hydrogen ions by the negative electrode, the hydrogen ions move to the positive electrode through the proton exchange membrane to undergo a reduction reaction with oxygen to generate water, and the energy required by a driving device is released. The PEMFCs have no pollutant emission, have the advantages of green and environment protection, and are one of important technical approaches for solving the energy problem. However, cathodic oxygen reduction (ORR) reaction kinetics are slow, requiring high platinum supported cathode catalysts to enhance the oxygen reduction reaction. Platinum, as a precious metal material, has an expensive price that increases the cost of PEMFCs, which is disadvantageous for large-scale applications of PEMFCs. In order to reduce the cost of the catalyst and reduce the consumption of noble metals, the improvement of the utilization rate of the noble metals is the key point of the research and development of the technology at present.
The platinum nanoparticles are susceptible to agglomeration during reduction of the support surface due to the high surface energy, which greatly reduces exposure of the active sites of the platinum particles and reduces the oxygen reduction (ORR) activity of the catalyst. Therefore, in order to optimize the utilization rate of noble metal platinum, a carrier material with high-efficiency platinum loading is needed to anchor the metal through the interaction between the carrier and the metal, and meanwhile, a high specific surface can provide sufficient sites for the deposition of metal particles, so that the agglomeration among the metal particles is reduced, the metal particles with fine and uniform dispersion of the particle size are synthesized on the surface of the carrier as much as possible, and the exposure of active sites is improved.
The characteristics of carbon, such as high specific surface area and good conductivity, and low cost, are important reasons for its choice as a platinum-based catalyst support material. Carbon black materials are the most widely used materials among the various types of carbon supports. However, the electron transport between their particle structures, the low surface activity is detrimental to the dispersed loading of platinum. The high specific surface area, good electrical conductivity, high crystallinity and excellent chemical stability of carbon nanotubes are good choices for its use as a support material. However, pure carbon nanotubes have inert surfaces, few active sites for supporting platinum metal and weak interaction. Platinum particles supported on the surface thereof are easily agglomerated. So the surface defects of the carbon nano tube material and the interaction between the carbon nano tube material and the metal-carrier are increased by methods such as acid treatment surface oxidation, etc., so that anchoring sites are provided for the carbon nano tube material to realize uniform dispersion, and meanwhile, the Pt utilization rate is improved. For example, patent 202210862367.9 discloses an alloy catalyst prepared by acidifying multiwall carbon nanotubes and then adding a metal salt solution for mixing and calcining. And adsorbing metal atoms by using the acidified carbon nano tube, depositing the metal on the surface of the carbon tube, anchoring the metal atoms through strong interaction, and finally preparing the alloy catalyst through heat treatment reduction. The patent 202210055155.X adopts a method of loading noble metal on carbon nano tubes and directly heating by using light irradiation, and directly heating by light irradiation to perform oxidation treatment, so that defects are formed on the surfaces of the carbon nano tubes, and the interaction of the noble metal on the surfaces of carriers is improved. Patent 202111148630.X uses carbon nano tube oxidized by potassium permanganate as carrier material to load platinum nano particles for preparing catalyst, and the hydrophilicity of the catalyst is improved by forming functional groups and defects by the oxidized carbon nano tube of potassium permanganate, and meanwhile, the water management phenomenon of the catalyst under high-current work is improved by adding the tubular structure of the carbon nano tube, but the oxidation treatment of the surface of the carbon tube causes a great deal of winding of the carrier, and the platinum particles are aggregated, so that the oxygen reduction performance of the catalyst in electrochemical work is seriously affected. Patent 200810069834.2 discloses a method for anchoring platinum catalyst by transition metal on carbon nanotubes, which comprises purifying carbon nanotubes by nitric acid, treating with mixed acid of hydrogen peroxide and concentrated sulfuric acid to obtain functionalized carbon nanotubes, and refluxing with platinum salt and transition metal salt solution to obtain the carbon nanotube supported alloy catalyst. According to the method, the surface defects of the carbon nanotubes are improved through surface functionalization of the carbon nanotubes, the interaction between metal and a carrier is enhanced, and the oxygen reduction activity of the catalyst is improved to a certain extent, but due to the aggregation of the oxidized carbon nanotubes, deposited metal particles are buried in a large amount, so that the utilization of noble metals is not facilitated, and the cost of the catalyst is greatly improved. Patent 201010562998.6 discloses a platinum catalyst supported by carbon nanotubes and a preparation method thereof, wherein the method adopts a platinum nanoparticle supported by mixing carbon nanotubes and chitosan. Although the surface acidification and oxidation treatment of the carbon nano tube are omitted, the surface of the carbon nano tube is perfect, so that the anchoring sites of metal particles on the surface of the carbon nano tube are insufficient, and a large amount of platinum particles are aggregated. Patent 202110366271.9 discloses a nano platinum catalyst taking a carbon nano tube as a carrier and a preparation method thereof, wherein potassium permanganate is adopted to oxidize, a layer of manganese oxide hydrophilic layer is coated on the surface of the carbon nano tube, and then the nano platinum catalyst is loaded by a reduction replacement method. The oxide coating layer is used for making up the hydrophobicity of the carbon nano tube, so that the surface of the prepared catalyst is converted into hydrophilicity, the dispersibility of the catalyst is improved, and the overall performance of the composite catalyst is enhanced. However, the coating of the surface oxide causes a decrease in the adsorption sites of platinum particles during the reduction process, which is disadvantageous in fully exerting the activity of platinum metal.
Disclosure of Invention
In order to overcome the defects and problems in the background art, graphene oxide connected to one end of a carbon nano tube is obtained through partial stripping of the carbon nano tube, and the graphene oxide formed by stripping and unfolding from one end of the carbon nano tube is continuously connected with the carbon nano tube under the action of chemical bonds to form a carbon material with a carbon nano tube connected graphene oxide structure. Functional groups and defects formed in the chemical stripping process can also strengthen the interaction between the noble metal and the carrier, and avoid the falling off and aggregation of the catalyst in the electrochemical process. Further, after the surface functionalization treatment is carried out on the carbon black, the surface of the carbon black is positively charged, and the carbon black and the negatively charged graphene oxide peeled off from the surface of the carbon nano tube are combined through electrostatic interaction and are embedded between graphene sheets to form a three-dimensional sandwich structure mixed carrier, the stacking of the graphene is further inhibited by the carbon black nano particles, the surface exposure of the composite material is improved, the uniform adhesion of noble metal on the surface of the carrier material in the synthesis process is facilitated, and the dispersibility of the noble metal on the surface of the carrier material is improved. The sandwich structure mixed carrier contains a large number of pores, facilitates mass transfer of electrolyte of a catalyst in a subsequent electrochemical process, greatly improves contact of the electrolyte with noble metal, accelerates diffusion rate of oxygen, improves the process of oxygen reduction, simultaneously provides a discharge channel for products in the subsequent electrochemical process of the fuel cell, prevents accumulation of the products from affecting subsequent reaction, and accelerates dynamic reaction process of the catalyst.
The invention aims to provide a sandwich structure carbon composite catalyst material with excellent conductivity and mass transfer property, low platinum loading and high platinum dispersibility, which consists of a mixed carrier with a sandwich structure and metal platinum. The sandwich structure hybrid carrier is characterized in that the sandwich structure hybrid carrier is formed by connecting a carbon nano tube-connected graphene material obtained by chemically stripping carbon nano tubes with carbon black subjected to surface modification (functionalization treatment). More specifically, the carbon black particles subjected to surface functionalization treatment are filled between carbon nano sheets, wherein the carbon nano sheets are sheets which are formed by partially chemically stripping graphene from multi-wall carbon nano tubes and are randomly and continuously distributed in a planar space; the carbon black after surface functionalization treatment has positive charges on the surface, is combined with nano-sheets with negative charges on the surface through static electricity, and is filled between the sheets to form a three-dimensional sandwich structure mixed carrier.
The surface of the sandwich-structure mixed carrier is graphitized, and the inside of the sandwich-structure mixed carrier is provided with rich pore channels, so that platinum can be efficiently loaded, and the platinum is uniformly dispersed and distributed on the surface of the carbon carrier.
The platinum in the sandwich-structure carbon composite carrier-supported platinum particle electrocatalyst material is supported on a sandwich mixed carrier by a conventional technology to obtain a uniformly platinum-supported composite catalyst material, as shown in fig. 4. The composite material not only realizes uniform platinum load, but also has extremely fine platinum particles, and simultaneously, a large number of pores of the structure of the composite material can effectively promote the mass transfer process, improve the exposure of active sites and effectively improve the oxygen reduction activity of the catalyst.
The other purpose of the present invention is to provide a preparation method of the platinum particle-supported electrocatalyst with a sandwich-structure carbon composite carrier, wherein platinum can be supported by chemical deposition of platinum in a dispersion liquid of the sandwich-structure carbon composite carrier, which belongs to the known technology, and the key point of the preparation method of the present invention is the preparation of the carrier, and the synthesis flow thereof is shown in fig. 1. The raw material carbon nanotube is a commercial raw material, as shown in fig. 2, is widely and easily available, and is firstly subjected to controllable oxidation corrosion to partially strip the wall of the carbon nanotube, so as to obtain the graphene-connected carbon nanotube material. A large number of functional groups and hole defects are formed on the surface of the carbon material in the chemical corrosion stripping process, as shown in fig. 3, which is beneficial to improving the interaction between the platinum nano particles and the carrier in the subsequent synthesis process, thereby strengthening the dispersion of platinum and improving the exposure of platinum active site atoms. The invention is characterized in that the functionalized carbon black and the graphene material connected with the carbon nano tube are compounded, so that the constructed sandwich structure can avoid the accumulation of nano sheets in the carrier in the reduction process.
In order to achieve the above object, the preparation method comprises the following steps:
(1) Adding the carbon nano tube and potassium permanganate into concentrated sulfuric acid solution, and stirring for a plurality of times;
(2) And (3) reacting the mixed solution obtained in the step (1) with hydrogen peroxide under the temperature control measure, and controlling the generation of reaction heat by adding ice water or removing heat in a low-temperature circulation way or controlling the material flow adding speed by using a micropump and the like until no bubbles are generated and the hydrogen peroxide is stopped being added. Then adding acid solution to remove impurities, stirring for a plurality of times, and centrifugally collecting sediment.
(3) Adding deionized water and an acid solution into the precipitate in the step (2), carrying out acid washing again, stirring for a plurality of times, washing with deionized water to be neutral, and filtering and drying to obtain the peeled carbon nano tube-graphene material.
(4) And dispersing a plurality of carbon black (ketjen black) by weight into the mixed solution of the surfactants to obtain carbon black suspension.
(5) Dispersing the carbon nano tube-graphene material in the step (3) into an aqueous solution, adding the aqueous solution into the carbon black suspension in the step (4), rapidly stirring, adding a reducing substance, reacting for a plurality of times, filtering, drying, and then annealing in a tube furnace to obtain the sandwich structure mixed support carrier material.
(6) Dispersing the mixed carrier in the step (5) into a solvent, then adding a chloroplatinic acid solution, stirring uniformly, adding a reducing agent for reduction treatment, continuously stirring, filtering, washing and drying to obtain the final electrocatalyst product.
Further, the diameter of the carbon nano tube in the step (1) is 8-15nm.
The acidic solution in step (2) and (3) is selected from dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid and the like, preferably hydrochloric acid.
The surfactant mixed solution in the step (4) consists of a cationic active agent, an emulsifying agent and chloride salt.
The mass ratio of the cationic active agent, the emulsifying agent, the chloride salt and the carbon black material is selected from 2-5:2-5:1-3:1.
the cationic active agent is selected from cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cationic polyacrylamide and the like, and preferably cetyl trimethyl ammonium chloride.
The emulsifier is selected from 2-amino-hydroxymethyl propane, trimethylol aminomethane, trimethyl amine, etc., preferably trimethylol aminomethane.
The chloride salt is selected from sodium chloride, potassium chloride and the like, preferably sodium chloride.
The mass ratio of the carbon black to the carbon nano tube-graphene material in the solution in the step (5) is selected from 1-4:1.
the reducing substance includes ascorbic acid, glucose, sodium formate, etc., preferably ascorbic acid.
The mass ratio of the reducing substance to the carbon nano tube graphene material is 10-15:1.
the stirring time is selected from 10-15h.
The solvent in the step (6) is selected from deionized water, glycol and a mixed solution of deionized water and glycol.
The reducing agent is selected from sodium borohydride, hydrazine hydrate and sodium citrate, preferably hydrazine hydrate.
The beneficial effects are that:
the invention adopts acidified carbon nano tube to oxidize and then directly peel off graphene oxide material from the surface of the carbon nano tube, and the graphene oxide is tightly connected with the carbon nano coil through conjugated chemical bonds. Compared with the patent CN 114804090A and the patent CN107904620A, the carbon nano tube graphene materials generated after single adsorption are more tightly connected, so that the corrosion resistance of the carrier material in the acid electrolyte for electrochemical testing can be improved.
According to the invention, through effectively designing the space structure of the carbon material, the active site enhancement effect of graphene, the high conductivity of the residual carbon nano tube and the pore structure support enhancement effect of carbon black particles are combined, so that the high dispersion load under the condition of low platinum content is realized, and the exposure of active atoms is promoted. The sandwich structure constructed by combining the graphene oxide with positive charges on the surface and negative charges stripped from the surface of the carbon nano tube through electrostatic interaction can avoid the accumulation of stripped carbon nano tube/graphene materials in the reduction process, further improve the adsorption nucleation sites of the carrier materials, and simultaneously improve the sufficient space for the diffusion of oxygen in the gap formed between the graphene sheets by the inserted carbon black particles, so that the oxygen reduction rate is accelerated, and the catalyst reaction rate is improved. The large amount of pore structures can also promote the transmission of electrolyte, so that the electrolyte is fully contacted with the active site, and the reaction kinetics rate of the catalyst is accelerated.
Drawings
FIG. 1 is a flow chart of a sandwich structure preparation provided by the invention.
FIG. 2 is a diagram of a carbon nanotube feedstock transmission electron microscope.
Fig. 3 is a transmission electron microscope image of a carbon nanotube after partial graphene is peeled off.
Fig. 4 is a platinum-carrying transmission electron microscope image of the composite activated carbon particles after the graphene is partially peeled off by the carbon nanotubes.
Fig. 5 is a carbon scan of the sample elements of fig. 4.
FIG. 6 is a comparison of the results of cyclic voltammogram tests of example 3, comparative example 1, comparative example 2, and JM 40% commercial platinum carbon catalysts provided herein.
FIG. 7 is a comparison of the results of polarization curve testing of example 3, comparative example 1, comparative example 2 and JM 40% commercial platinum carbon catalysts provided herein.
Detailed Description
The technical solution of the patent is further described with reference to the above figures and specific embodiments.
Example one:
adding 1g of multi-wall carbon nano tube into 100ml of concentrated sulfuric acid solution, magnetically stirring for 30min, slowly adding 6g of potassium permanganate into the mixed solution under ice bath environment, vigorously stirring at normal temperature for 4h, draining into 1000ml of ice water through a glass rod, waiting for melting of the ice water, adding hydrogen peroxide into the diluted solution until no bubbles are generated, stopping adding hydrogen peroxide, stirring for 10min, adding 10ml of concentrated hydrochloric acid solution into the mixed solution, magnetically stirring for 1h, then adding the collected precipitate into the diluted hydrochloric acid solution for further pickling, dialyzing for two days by using a dialysis bag, and freeze-drying to obtain the carbon nano tube-graphene material.
Adding 900mg of cetyl trimethyl ammonium bromide, 900mg of tris (hydroxymethyl) aminomethane and 600mg of sodium chloride into 200ml of deionized water, ultrasonically stirring for 1h, adding 200mg of carbon black material, and magnetically stirring for 3h to obtain a suspension A; adding 100mg of carbon nano tube and graphene material into 200ml of deionized water, and performing ultrasonic dispersion for 1h to obtain a dispersion liquid B; and pouring the dispersion liquid B into the stirred suspension liquid A, stirring for 10 hours, adding 2g of ascorbic acid, stirring for 12 hours at 90 ℃, centrifuging, washing and drying to obtain the mixed carrier.
Weighing 75mg of mixed carrier, adding the mixed carrier into 150ml of mixed solution of deionized water and ethylene glycol (the water-alcohol ratio is 1:1), performing ultrasonic dispersion for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, continuously stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the platinum catalyst carried by the mixed carrier.
Example two:
250mg of cetyltrimethylammonium bromide, 250mg of tris and 120mg of sodium chloride are added into 100ml of deionized water, ultrasonic stirring is carried out for 1h, then 100mg of carbon black material is added, and magnetic stirring is carried out for 3h, thus obtaining suspension A; adding 100mg of carbon nano tube and graphene material into 200ml of deionized water, and performing ultrasonic dispersion for 1h to obtain a dispersion liquid B; and pouring the dispersion liquid B into the stirred suspension liquid A, stirring for 10 hours, adding 2g of ascorbic acid, stirring for 12 hours at 90 ℃, centrifuging, washing and drying to obtain the mixed carrier.
Weighing 75mg of mixed carrier, adding the mixed carrier into 150ml of mixed solution of deionized water and ethylene glycol (the water-alcohol ratio is 1:1), performing ultrasonic dispersion for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, continuously stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the platinum catalyst carried by the mixed carrier.
Example three:
adding 500mg of cetyltrimethylammonium bromide, 500mg of tris (hydroxymethyl) aminomethane and 240mg of sodium chloride into 200ml of deionized water, ultrasonically stirring for 1h, then adding 200mg of carbon black material, and magnetically stirring for 3h to obtain a suspension A; adding 100mg of carbon nano tube and graphene material into 200ml of deionized water, and performing ultrasonic dispersion for 1h to obtain a dispersion liquid B; and pouring the dispersion liquid B into the stirred suspension liquid A, stirring for 10 hours, adding 2g of ascorbic acid, stirring for 12 hours at 90 ℃, centrifuging, washing and drying to obtain the mixed carrier.
Weighing 75mg of mixed carrier, adding the mixed carrier into 150ml of mixed solution of deionized water and ethylene glycol (the water-alcohol ratio is 1:1), performing ultrasonic dispersion for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, continuously stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the platinum catalyst carried by the mixed carrier.
Example four:
adding 1g of cetyltrimethylammonium bromide, 1g of tris (hydroxymethyl) aminomethane and 0.8g of sodium chloride into 200ml of deionized water, ultrasonically stirring for 1h, then adding 400mg of carbon black material, and magnetically stirring for 3h to obtain a suspension A; adding 100mg of carbon nano tube and graphene material into 400ml of deionized water, and performing ultrasonic dispersion for 1h to obtain a dispersion liquid B; and pouring the dispersion liquid B into the stirred suspension liquid A, stirring for 10 hours, adding 2g of ascorbic acid, stirring for 12 hours at 90 ℃, centrifuging, washing and drying to obtain the mixed carrier.
Weighing 75mg of mixed carrier, adding the mixed carrier into 150ml of mixed solution of deionized water and ethylene glycol (the water-alcohol ratio is 1:1), performing ultrasonic dispersion for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, continuously stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the platinum catalyst carried by the mixed carrier.
Example five:
adding 500mg of cetyltrimethylammonium chloride, 500mg of 2-amino-hydroxymethyl propane and 240mg of sodium chloride into 200ml of deionized water, ultrasonically stirring for 1h, then adding 200mg of carbon black material, and magnetically stirring for 3h to obtain a suspension A; adding 100mg of carbon nano tube and graphene material into 200ml of deionized water, and performing ultrasonic dispersion for 1h to obtain a dispersion liquid B; and pouring the dispersion liquid B into the stirred suspension liquid A, stirring for 10 hours, adding 2g of ascorbic acid, stirring for 12 hours at 90 ℃, centrifuging, washing and drying to obtain the mixed carrier.
Weighing 75mg of mixed carrier, adding the mixed carrier into 150ml of mixed solution of deionized water and ethylene glycol (the water-alcohol ratio is 1:1), performing ultrasonic dispersion for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, continuously stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the platinum catalyst carried by the mixed carrier.
Comparative example one:
weighing 75mg of multi-wall carbon nano tube material, dispersing the multi-wall carbon nano tube material into 150ml of mixed solution of deionized water and ethylene glycol (the water-alcohol ratio is 1:1), performing ultrasonic dispersion for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, continuously stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the carbon nano tube platinum-carrying catalyst.
Comparative example two:
weighing 75m of carbon nano tube and graphene material, dispersing the material into 150ml of mixed solution of deionized water and ethylene glycol (the water-alcohol ratio is 1:1), performing ultrasonic dispersion for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, continuously stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the carbon nano tube and graphene supported platinum catalyst.
Comparative example three:
adding 25mg of carbon nano tube and graphene material into 150ml of deionized water, performing ultrasonic dispersion for 1h, slowly adding 50mg of carbon black material under the condition of rapid stirring, fully stirring, adding 500mg of ascorbic acid, stirring for 5h, filtering, washing and drying to obtain the mixed carrier.
Dispersing the solid after the reaction into 150ml of a mixed solution of deionized water and glycol (the water-alcohol ratio is 1:1), super-dispersing for 1h, adding 5ml of chloroplatinic acid solution (10 mg/ml) under rapid stirring, stirring for 5h, adding 600ul of 85% hydrazine hydrate solution for reduction for 1h, centrifuging, washing and drying, and collecting the mixture to obtain the platinum catalyst carried by the mixed carrier.
Catalyst Performance test
2mg of catalyst was uniformly dispersed in a mixture solution containing 660ul of deionized water, 330ul of isopropyl alcohol and 10ul 0.5wt%Nafion solution for 30min by ultrasound to form uniform catalyst ink, and then 20ul of ink solution was measured out to drop onto the surface of the glassy carbon electrode using a pipette until a uniform film was formed. The glassy carbon electrode was polished to a mirror surface on a chamois leather using 0.5nm alumina polishing powder prior to each experiment. A drop of 0.1m HClO4 solution with saturated nitrogen was first added dropwise to the catalyst film before electrochemical measurement to wet the catalyst. Subsequently, in an N2 saturated 0.1M HClO4 solution, a scan rate of 50mV was performed from 0.03 to 1.1V (relative to RHE) until a stable voltammogram was obtained in an N2 saturated 0.1M HClO4 electrolyte, the last cycle was taken as a Cyclic Voltammogram (CV) of the catalyst, then an LSV test was performed in an N2 saturated 0.1M HClO4 electrolyte at 1600rpm at a scan rate of 10mV from 0.1 to 1.1V (relative to RHE), then oxygen was introduced into the electrolyte for 30min, and an LSV test was performed in an O2 saturated 0.1M HClO4 electrolyte at a scan rate of 10mV from 0.1 to 1.1V (relative to RHE) at 1600rpm, to obtain a polarization curve of the catalyst.
The performance indices obtained from the tests of the catalysts prepared in the examples and comparative examples and the commercial platinum carbon catalysts are shown in the following table:
JM 40% Pt/C is a commercial platinum carbon catalyst from Johnson Matthey, inc. with a platinum content of 40%.
As shown in fig. 1, the specific surface area of the peeled multiwall carbon nanotubes can be significantly improved by peeling the carbon nanotubes to obtain the carbon nanotube-graphene material. Meanwhile, the surface of the peeled graphene oxide contains a large number of functional groups and defects, so that a large number of anchor points are provided for the subsequent deposition of noble metal particles, and the interaction between the carrier and the noble metal is further enhanced. Secondly, the surface of the carbon black is positively charged by treating the carbon black with a surfactant, so that the carbon black is promoted to be embedded into the carbon nano tube and the graphene material, the stacking effect of the material is isolated, and meanwhile, the constructed sandwich structure can play a role in promoting the transmission of electrolyte, so that the electrolyte is fully contacted with an active site.
Comparison graphs of cyclic voltammogram test results for example 3, comparative example 1, comparative example 2, and JM 40% commercial platinum carbon catalyst as shown in fig. 6. The electrochemical active area of the catalyst (comparative example 2) prepared by loading platinum nanoparticles with carbon nanotube-graphene materials is far larger than that of the original carbon nanotube-loaded platinum catalyst (comparative example 1), which shows that graphene obtained by stripping carbon nanotubes is stacked, but the carbon nanotube-graphene materials obtained by stripping still have larger specific surface area and larger electrochemical active area than those of the original carbon nanotubes due to the blocking effect to a certain extent of the existence of the carbon nanotubes. Meanwhile, according to the comparative example 3 and the comparative example 2, the embedding of the carbon black material truly prevents the stacking of the carbon nano tube and the graphene material greatly, the electrochemical activity area of the catalyst prepared by loading platinum nano particles with the carbon nano tube and the graphene material embedded by the carbon black is further improved, and the electrochemical activity area (ECSA) of the catalyst (example 3) with the platinum nano particles loaded in the sandwich structure is also obviously larger than that of the catalyst with JM 40% commercial platinum carbon, so that the advantage of the structure of the large specific surface area is further illustrated.
The catalysts were then subjected to LSV testing at a scan rate of 10mV from 0.1 to 1.1V (versus RHE) in a 0.1M HClO4 electrolyte at 1600rpm under saturated oxygen and the data collected to prepare polarization curve comparison plots for the example 3, comparative example 1, comparative example 2 and JM 40% commercial platinum carbon catalysts shown in FIG. 7. In the figure, the half-wave potential corresponding to the example 3 is far greater than that of the comparative example 2 and the commercial platinum-carbon catalyst, which shows that the embedding of the carbon black material improves the specific surface area of the carbon carrier, thereby improving the adhesion site of the noble metal on the surface of the carrier material, strengthening the anchoring of the noble metal, and meanwhile, the construction of the sandwich structure accelerates the oxygen transmission, improves the reduction rate of the oxygen, accelerates the mixing dynamics rate of the catalyst, ensures that the mixing dynamics-diffusion control area of the catalyst is obviously moved to the right, and the half-wave potential is increased.
Claims (9)
1. A sandwich structure mixed carbon carrier supported platinum particle electrocatalyst is composed of a sandwich structure mixed carrier and metal platinum. The sandwich-structured hybrid carrier is characterized in that the sandwich-structured hybrid carrier is formed by connecting a carbon nano tube-connected graphene material obtained by chemically stripping carbon nano tubes with carbon black subjected to surface modification.
2. The sandwich structure mixed carbon carrier supported platinum particle electrocatalyst is characterized in that the sandwich structure mixed carrier is formed by filling carbon black particles subjected to functionalization treatment between carbon nano sheet layers, wherein the carbon nano sheet is a sheet layer which is formed by partially chemically stripping multi-wall carbon nano tubes into graphene and is randomly and continuously distributed in a planar space.
3. The sandwich structure mixed carbon carrier supported platinum particle electrocatalyst is characterized in that the surface of the sandwich structure mixed carrier is graphitized, and the inside of the sandwich structure mixed carrier is provided with rich pore channels, so that platinum can be efficiently supported, and the platinum is uniformly dispersed on the surface of the carbon carrier.
4. A preparation method of a sandwich structure mixed carbon carrier supported platinum particle electrocatalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Adding the carbon nano tube and potassium permanganate into concentrated sulfuric acid solution, and stirring for a plurality of times;
(2) And (3) reacting the mixed solution obtained in the step (1) with hydrogen peroxide under the temperature control measure, and controlling the generation of reaction heat by adding ice water or removing heat in a low-temperature circulation way or controlling the material flow adding speed by using a micropump and the like until no bubbles are generated and the hydrogen peroxide is stopped being added. Then adding acid solution to remove impurities, stirring for a plurality of times, and centrifugally collecting sediment.
(3) And (3) adding an acid solution into the precipitate in the step (2) for acid washing again, stirring for a plurality of times, centrifuging to be neutral by using deionized water, filtering and drying to obtain the exfoliated carbon tube graphene material.
(4) And dispersing a plurality of carbon black in a mixed solution of the surfactant to obtain a carbon black suspension.
(5) Dispersing the carbon nano tube-graphene material in the step (3) into an aqueous solution, adding the aqueous solution into the carbon black suspension in the step (4), rapidly stirring, adding a reducing substance, stirring for a plurality of times, filtering, and drying to obtain the sandwich structure mixed support carrier material.
(6) Dispersing the mixed carrier in the step (5) into a solvent, then adding a chloroplatinic acid solution, stirring uniformly, adding a reducing agent for reduction treatment, continuously stirring, filtering, washing and drying to obtain a final product.
5. The method for preparing the sandwich structure mixed carbon carrier supported platinum particle electrocatalyst according to claim 4, wherein the diameter of the carbon nanotube in step (1) is in the range of 8-50 nm;
the ratio range of the carbon nano tube to the potassium permanganate is selected from 1:6-8.
The stirring time is 2-10 h.
6. The method for preparing the sandwich structure mixed carbon carrier supported platinum particle electrocatalyst according to claim 4, wherein the acidic solution in steps (2) and (3) is selected from dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, and the like.
7. The method for preparing the sandwich structure mixed carbon carrier supported platinum particle electrocatalyst according to claim 4, wherein the surfactant mixed solution in step (4) comprises a cationic active agent, an emulsifying agent and a chloride salt; the mass ratio of the cationic active agent, the emulsifying agent, the chloride salt and the carbon black material is selected from 2-5:2-5:1-3:1.
the cationic active agent is selected from cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cationic polyacrylamide and the like;
the emulsifier is selected from 2-amino-hydroxymethyl propane, trimethylol aminomethane, trimethyl amine and the like;
the chloride salt is selected from sodium chloride, potassium chloride and the like.
8. The method for preparing the sandwich structure mixed carbon carrier supported platinum particle electrocatalyst according to claim 4, wherein the concentration of the carbon nanotube-graphene dispersion liquid in step (5) is selected from 0.5-1mg/ml;
stirring for 10-15 hr;
reducing substances include glucose, sodium formate, ascorbic acid, etc.;
the mass ratio of the reducing substance to the carbon tube-connected graphene is 10-20: 1.
9. the method for preparing a sandwich structure mixed carbon carrier supported platinum particle electrocatalyst according to claim 4, wherein the solvent in step (6) is selected from deionized water, ethanol, ethylene glycol, and isopropanol; the concentration of the chloroplatinic acid solution is 10mg/ml; the reducing agent is selected from sodium borohydride, hydrazine hydrate and sodium citrate;
the drying mode is freeze drying.
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