CN112993278A - Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof - Google Patents
Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title claims description 13
- 229910045601 alloy Inorganic materials 0.000 title claims description 4
- 239000000956 alloy Substances 0.000 title claims description 4
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
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- 238000000034 method Methods 0.000 claims description 13
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- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
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- 238000012545 processing Methods 0.000 description 4
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- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 3
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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Images
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
-
- 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
- H01M4/8803—Supports for the 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparation method of a flower-shaped titanium dioxide/reduced graphene composite carrier with high specific surface and high conductivity, and application of a platinum-supported and platinum alloy electrocatalyst thereof2And compounding the prepared flower-shaped titanium dioxide precursor with graphene oxide, and treating in a reducing atmosphere to obtain the flower-shaped titanium dioxide/reduced graphene composite carrier. The flower-like titanium dioxide/reduced graphene composite carrier obtained by the preparation method is high in conductivity and good in stability, the three-dimensional structure is beneficial to the transmission of reactants, and the preparation method is simple in preparation process and easy to amplify. The flower-shaped titanium dioxide/reduced graphene composite carrier has excellent catalytic activity and stability for the oxygen reduction reaction of the fuel cell after carrying platinum or platinum alloy active components.
Description
Technical Field
The invention relates to a fuel cell electrocatalyst and a preparation method thereof, in particular to a catalyst carrier with high catalytic activity and stability for oxygen electrochemical reduction reaction and a preparation method of the catalyst, belonging to the technical field of inorganic materials.
Background
The fuel cell is a reaction device for directly converting chemical energy of fuel into electric energy, and has the characteristics of high specific energy, high energy conversion rate, environmental friendliness and the like. The performance and cost of electrocatalysts, which are key materials for fuel cells, are critical factors affecting the practical use of devices. Therefore, the development of a highly active and stable electrocatalyst is of great significance for the industrialization of fuel cell technology.
Currently, metallic platinum (Pt) is widely used as a fuel cell electrocatalyst due to its high electrocatalytic activity. In order to improve the utilization rate of Pt, the practical electrocatalyst is formed by loading highly dispersed Pt nano particles on the surface of a carbon carrier. The carbon black material has high surface area, good conductivity, porous structure and appropriate surface hydrophilicity and hydrophobicity, thus becoming one of the best materials for the electrocatalyst carrier. However, the conventional carbon material is rich in defects and functional groups on the surface, and is easy to generate oxidation corrosion (C + H) under the actual working condition of strong acid and high potential of the fuel cell2O→CO2+4H++4e-Rhe,25 ℃), resulting in Pt nanoparticles running off, agglomerating, causing fuel cell performance degradation. Therefore, the development of a corrosion-resistant fuel cell carrier is critical to improving the life of the fuel cell.
TiO2The titanium oxide has excellent stability and corrosion resistance under an acidic medium and a high potential, and is expected to be used as an electrocatalyst carrier, but the titanium oxide is used as a semiconductor and has poor conductivity, so that the titanium oxide cannot be applied to an electrocatalyst. Chinese patent publication No. CN105727998B discloses a titanium dioxide nanoflower photocatalytic material coated with a noble metal nanodot cadmium sulfide film, comprising the following steps: (1) adding tetrabutyl titanate into a hydrochloric acid solution, putting FTO conductive glass into a high-pressure reaction kettle, and carrying out heat treatment to obtain an FTO electrode loaded with nano flower-shaped titanium dioxide; (2) and depositing noble metal nano dots on the FTO and coating a cadmium sulfide film. In the patent, the titanium oxide nanoflower is assembled by titanium oxide nanorods, and the titanium oxide nanoflower is used as a semiconductor photocatalyst and has good performance of producing hydrogen by photoelectrocatalysis. The literature (Energy environ. sci.,2011,4, 4079; j. mater. chem.,2012,22, 7910) reports that a nanorod composed of titanium oxide nanoparticles is further assembled into a structure of a nanoflower as a structure of a nanoflowerThe photocatalyst has excellent performance in dye-sensitized solar cells. The method comprises the following steps: and carrying out hydrothermal reaction on a mixture of tetrabutyl titanate and glacial acetic acid to obtain a powder sample, and carrying out centrifugal washing, drying and roasting to obtain the titanium dioxide nanoflower assembled by the nanorods. The literature (International Journal of Hydrogen Energy,2017,42,5948) reports a TiO compound2(B) And anatase TiO2The nanoflower assembled by the coexisting nanosheets is used for methanol electrooxidation reaction after being loaded with a platinum catalyst. The method comprises the following steps: mixing tetrabutyl titanate and acetic acid, carrying out hydrothermal reaction, centrifugally washing, drying and roasting a product to obtain TiO2(B) And anatase TiO2And the coexisting nano sheets are assembled into the nanoflower.
As can be seen from the above reports, TiO2The semiconductor is widely applied to photocatalysis, but the semiconductor still has the problems of poor conductivity, insufficient surface area and the like when being used as an electrocatalyst carrier. To TiO 22The TiO content can be improved to a certain extent by doping hetero atoms or making oxygen defects2The conductivity of (a); however, the material is difficult to maintain three-dimensional morphology and large specific surface area due to the processes of hydrogen atmosphere treatment, high-temperature roasting and the like. Thus preparing TiO with high conductivity and high specific surface area2It remains a challenge to apply to fuel cell carriers.
The invention content is as follows:
aiming at the defects of the prior art, the invention aims to provide a preparation method of a flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and an alloy electrocatalyst thereof with high specific surface and high conductivity, and the preparation method has strong universality, simple process and easy amplification.
In order to achieve the purpose, the invention adopts the following specific scheme to realize:
a preparation method of a flower-shaped titanium dioxide and reduced graphene composite carrier supported platinum and platinum alloy catalyst is characterized by compounding a prepared flower-shaped titanium dioxide precursor with graphene oxide, processing the mixture in an atmosphere to obtain a flower-shaped titanium dioxide/reduced graphene composite carrier, and depositing platinum or platinum alloy nanoparticles on the surface of the flower-shaped titanium dioxide/reduced graphene composite carrier.
Further, flower-like titanium dioxide precursor (p-TiO)2) Is synthesized by a hydrothermal method. Specifically, hydrolyzing n-butyl titanate in glacial acetic acid to obtain a milky solution, heating the milky solution in a hydrothermal kettle to obtain a milky precipitate, and centrifugally washing and drying the milky precipitate to obtain a flower-like titanium dioxide precursor;
preferably, the volume ratio of tetrabutyl titanate to glacial acetic acid is 1:3 to 1: 100;
preferably, the hydrothermal temperature is 120-180 ℃;
preferably, the hydrothermal time is 8 to 48 hours;
further, Graphene (GO) is obtained by reducing graphite powder in a strongly acidic solution. Specifically, adding graphite powder into concentrated nitric acid and concentrated sulfuric acid, then adding potassium permanganate, adding water while stirring, heating to 80-99 ℃, and keeping the temperature for 60min to obtain GO; centrifuging and washing the sample to neutrality by using deionized water, and performing freeze drying to collect GO powder;
preferably, the mass ratio of the graphite powder to the concentrated nitric acid is 1:30 to 1: 3;
preferably, the mass ratio of the graphite powder to the concentrated sulfuric acid is 1:100 to 1: 10;
preferably, the mass ratio of the graphite powder to the potassium permanganate is 5:1 to 1: 3;
further, adding graphene GO powder into water according to a certain proportion, and ultrasonically dispersing the graphene GO powder into a golden yellow transparent solution, wherein preferably, the concentration of the GO aqueous solution is 0.5-3mg mL-1；
Further, adding a flower-like titanium dioxide precursor p-TiO into the GO aqueous solution2Ultrasonically mixing uniformly until the sample turns brown and is uniformly dispersed in water, and then carrying out freeze drying to obtain a flower-shaped titanium dioxide precursor/graphene compound;
preferably, GO is reacted with p-TiO2In a mass ratio of 3:175 to 60:175
Further, treating the composite of the flower-shaped titanium dioxide precursor/graphene at a certain atmosphere and temperature to obtain flower-shaped titanium dioxide/reductionGraphene composite carrier TiO2@RGO；
Preferably, the atmosphere may be hydrogen gas or a mixed gas of hydrogen gas and an inert gas;
preferably, the treatment temperature is 500-1000 ℃;
preferably, the treatment time is 1 to 5 hours;
further, the platinum-loaded flower-like titanium dioxide/reduced graphene is prepared by an ethylene glycol reduction method, specifically, NaOH is added into an ethylene glycol solution of chloroplatinic acid, and the pH value of the solution is adjusted to 8-14; heating the mixed solution to 130-160 ℃, preserving the heat for 0.5-6 hours, and adding TiO in proportion after the solution is cooled to room temperature2@ RGO composite carrier, adding inorganic acid to adjust pH to 4-7 and stirring the solution for 1-24 hr, filtering and washing the sample, and vacuum drying to obtain Pt-TiO2@ RGO sample;
preferably, the concentration of the ethylene glycol solution of chloroplatinic acid is 0.5 to 10 mg of platinum per ml;
preferably, the inorganic acid may be hydrochloric acid or sulfuric acid or nitric acid;
further, the flower-like titanium dioxide/reduced graphene loaded with the platinum alloy is prepared by an ethylene glycol reduction method, specifically, NaOH is added into an ethylene glycol solution of chloroplatinic acid and transition metal salt, and the pH value of the solution is adjusted to 8-14; heating the mixed solution to 130-180 ℃, preserving the heat for 0.5-6 hours, and adding TiO in proportion after the solution is cooled to room temperature2@ RGO composite carrier, adding inorganic acid to adjust pH to 4-7 and stirring the solution for 1-24 hr, filtering and washing the sample, and vacuum drying to obtain Pt-TiO2@ RGO sample;
preferably, the transition metal salt may be a nitrate or chloride salt of Fe, Co and Ni.
Compared with the prior art, the invention has the following advantages and effects:
TiO prepared by the invention2The @ RGO carrier has large specific surface area, good conductivity and high active component loading, and is an excellent electrocatalyst carrier. The carrier is one after carrying Pt or Pt alloyThe catalyst has high electrochemical catalytic activity and stability for oxygen reduction reaction. The preparation method is simple in preparation process, suitable for large-scale production and has a remarkable application prospect.
Description of the drawings:
FIG. 1 Scanning Electron Microscope (SEM) image of a sample prepared in example 2.
FIG. 2 Scanning Electron Microscope (SEM) image of the sample prepared in example 7.
FIG. 3A Transmission Electron Micrograph (TEM) of a sample obtained in example 7.
FIG. 4X-ray diffraction patterns (XRD) of samples obtained in examples 2 and 7.
FIG. 5 results of resistivity tests of catalysts obtained in examples 4, 5 and 6.
FIG. 6 comparison of oxygen reduction polarization curves before and after cycling test (oxygen conditions, 0.6-1.0V vs. reversible hydrogen electrode, 10000 cycles) for the sample prepared in example 7 and a commercial Pt/C catalyst (Zhuangxinwan). And (3) testing conditions are as follows: oxygen saturated 0.1M HClO4Electrode rotation speed 1600rpm, sweep rate: 10mV s-1。
Detailed Description
The invention is further illustrated below with reference to specific examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Dissolving 2mL of n-butyl titanate in 60mL of glacial acetic acid, and uniformly stirring to obtain a milky white solution; and heating the mixed solution to 140 ℃ in a hydrothermal kettle, and keeping the temperature for 12 h. After the hydrothermal kettle is naturally cooled, obtaining milk white colloid or precipitate or the mixture of the milk white colloid and the precipitate, centrifugally washing the obtained milk white colloid or precipitate with deionized water, and finally drying the obtained product to obtain white flower-shaped TiO2Precursor p-TiO2。
Example 2
Flower-like TiO obtained in example 12Precursor p-TiO2Heating in air atmosphere at a heating rate of 2 deg.C for 2 min-1Heating to 500 deg.C and maintaining for 3h, cooling to room temperature to obtain flower-like TiO2And (3) sampling. As can be seen from the SEM of the sample in FIG. 1, the sample appeared to be formed of TiO2TiO assembled by nanosheets2The nanometer flower is shaped. As can be seen from the X-ray diffraction pattern of the sample of FIG. 4, this sample is good anatase TiO2A crystal structure.
Example 3
Weighing 1g of graphite powder, adding the graphite powder into a round-bottom flask, sequentially and slowly adding 20mL of concentrated nitric acid and 80mL of concentrated sulfuric acid, and uniformly stirring the mixed solution; 3g of potassium permanganate is weighed and slowly added into the solution, and the solution is uniformly stirred; weighing 80mL of deionized water, slowly adding the deionized water into the mixed solution under stirring, and uniformly stirring; heating the obtained solution to 98 ℃ and preserving heat for 60min to obtain Graphene Oxide (GO) dispersion liquid; and centrifugally washing the sample to be neutral by deionized water, and freeze-drying to obtain a GO powder sample.
Example 4
24mg of GO obtained in example 3 is weighed, dissolved in 24mL of deionized water, ultrasonically dispersed to obtain a golden yellow colloidal solution, and 239mg of p-TiO obtained in example 1 is added2And ultrasonically mixing uniformly to obtain brown suspension, and finally freeze-drying, collecting and grinding the sample to obtain the sample p-TiO2@ GO 15%. Then H is added2Processing for 3 hours at 500 ℃ in the atmosphere of/Ar to obtain TiO2@ RGO 15% sample.
Example 5
Weighing 40mg of GO obtained in example 3, dissolving in 40mL of deionized water, performing ultrasonic dispersion to obtain a golden yellow colloidal solution, and adding 211mg of p-TiO obtained in example 12And ultrasonically mixing uniformly to obtain brown suspension, and finally freeze-drying, collecting and grinding the sample to obtain the sample p-TiO2@ GO 25%. Then H is added2Processing for 3 hours at 500 ℃ in the atmosphere of/Ar to obtain TiO2@ RGO 25% sample.
Example 6
56mg of GO obtained in example 3 is weighed and dissolved in 56mL of deionized water, then the solution is subjected to ultrasonic dispersion to obtain a golden yellow colloidal solution, and 182mg of p-TiO obtained in example 1 is added2And ultrasonically mixing uniformly to obtain brown suspension, and finally freeze-drying, collecting and grinding the sample to obtain the sample p-TiO2@ GO 35%. Then H is added2Processing for 3 hours at 500 ℃ in the atmosphere of/Ar to obtain TiO2@ RGO 35% sample.
Example 7
Measuring 13.33mL of chloroplatinic acid/ethylene glycol solution (the concentration of Pt is 1.5mg/mL), adding the chloroplatinic acid/ethylene glycol solution into 20mL of ethylene glycol solution, uniformly stirring, adding 10mL of 1M NaOH ethylene glycol solution, and uniformly stirring; heating the mixed solution to 140 ℃ in an oil bath and preserving heat for 4 hours; after the solution had cooled to room temperature, 80mg of TiO from example 4 was added2@ RGO carrier is evenly stirred, then HCl aqueous solution with the concentration of 1M is added to adjust the pH value of the mixed solution to 4-7, after stirring for 4h, the sample is filtered, washed and dried in vacuum, and the titanium dioxide nanoflower/reduced graphene sample Pt-TiO carrying platinum nano particles is obtained2@ RGO. From the SEM image of the sample in FIG. 2, TiO loaded with Pt nanoparticles2The flower-shaped structure of the nanometer flower is well reserved; from the transmission electron micrograph of the sample of FIG. 3, TiO2Platinum particles with the particle size of 2-3 nanometers are supported on the surface of the catalyst, and the platinum particles are arranged on TiO2The surface distribution is uniform. From the X-ray diffraction patterns of the samples in FIG. 4, except for TiO in the samples2The diffraction peak of (2) also shows a weak diffraction peak of the Pt (111) crystal face at a diffraction angle of about 40 °, and the weak diffraction peak also shows that the granularity of platinum is small.
Example 8
Measuring 12.11mL of ethylene glycol solution of chloroplatinic acid (the concentration of Pt is 1.5mg/mL) and 0.365mL of ethylene glycol solution of cobalt acetate (the concentration of Co is 5mg/mL), adding the ethylene glycol solution into 20mL of ethylene glycol solution, uniformly stirring, adding 10mL of 1M NaOH ethylene glycol solution, and uniformly stirring; heating the mixed solution to 140 ℃ in an oil bath and preserving heat for 4 hours; after the solution had cooled to room temperature, 80mg of TiO obtained as described in example 4 were added2@ RGO carrier and stirring well, then adding hydrochloric acid solution with concentration of 1MAdjusting the pH value of the mixed solution to 4-7, stirring for 4h, filtering and washing a sample, and drying in vacuum to obtain Pt3Co-TiO2@ RGO sample.
Effects of the implementation
As is clear from the resistance values of the samples obtained in examples 4, 5 and 6 in FIG. 5, the values were determined depending on TiO2The content of the @ RGO composite species reduced graphene is increased, the resistance value of the sample is obviously reduced, and the conductivity is improved. From the comparison of catalytic activity of example 7 and the comparative commercial Pt/C on oxygen reduction in FIG. 6, it can be seen that, although the initial half-wave potential of the commercial Pt/C on oxygen reduction is more positive than that of example 7 by 10mV, the oxygen reduction half-wave potential of the commercial Pt/C is reduced by about 40mV after 10000 cycles, while the catalyst of example 7 is not substantially reduced, showing good catalytic stability.
Claims (5)
1. A platinum and alloy catalyst supported by a flower-shaped titanium dioxide/reduced graphene composite carrier, and a preparation method and application thereof are characterized in that the method comprises the following steps:
(1) glacial acetic acid and tetrabutyl titanate generate a flower-shaped titanium dioxide precursor through a hydrothermal reaction;
(2) dispersing a flower-shaped titanium dioxide precursor in water, and compounding the flower-shaped titanium dioxide precursor with graphene oxide under the ultrasonic action of a cell crusher to obtain a titanium dioxide precursor/graphene oxide compound;
(3) carrying out thermal reduction treatment on the titanium dioxide precursor/graphene oxide compound obtained in the step (2) in an atmosphere containing hydrogen to obtain a titanium dioxide/reduced graphene compound;
(4) and (3) loading Pt or Pt alloy obtained by an ethylene glycol reduction method on the surface of the titanium dioxide/reduced graphene composite carrier obtained in the step (3) to obtain a flower-shaped titanium dioxide/reduced graphene composite carrier-loaded platinum or Pt alloy catalyst.
2. The method as claimed in claim 1, wherein the flower-like titanium dioxide precursor in step (1) is prepared by hydrothermal reaction at 120-180 ℃ for 8-48 hours using glacial acetic acid and tetrabutyl titanate as reactants.
3. The method according to claim 1, wherein the titanium dioxide precursor/graphene oxide composite in step (2) is the flower-like titanium dioxide precursor generated in step (1) and has a concentration of 0.5 to 3mg ml-1The high-dispersion graphene oxide solution is realized by an ultrasonic dispersion method.
4. The preparation method according to claim 1, wherein the titanium dioxide/reduced graphene composite support in the step (3) is prepared by heating at a heating rate of 1-10 ℃ for min in a reducing atmosphere containing hydrogen gas-1Heating the sample in the step (2) to 500-1000 ℃ and preserving the temperature for 1-5 hours.
5. The preparation method according to claim 1, wherein in the step (4), the Pt or Pt alloy nanoparticles are prepared by an ethylene glycol method and loaded on the surface of the flower-shaped titanium dioxide/reduced graphene composite carrier, and the loading amount of the Pt or Pt alloy active component is 5-80 wt.%.
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