CN115663208A - Pt-CuGaO for direct methanol fuel cell anode 2 /C composite catalyst and preparation method thereof - Google Patents
Pt-CuGaO for direct methanol fuel cell anode 2 /C composite catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Pt-CuGaO for a direct methanol fuel cell anode 2 a/C composite catalyst and a preparation method thereof; the catalyst is prepared by ABO 2 The delafossite copper gallium oxide with the structure is used as a carrier of nano platinum, and the load of the nano platinum is 5-15wt.%; during preparation, the Cu-Ga oxide carrier is synthesized by a hydrothermal method, nano platinum is reduced by a polyalcohol thermal method, and carbon powder is loaded by a microwave batch reaction method to obtain the high-efficiency and stable Pt-CuGaO 2 5wt.% of the catalyst gave 653.4mA/mg Pt ‑1 Mass activity, 2.53mA/cm 2 Specific activity of 25.83m 2 (iv) electrochemical active area of/g, indications of forward peak current density and reverse peak current density against carbon monoxide poisoningRatio (I) f /I b ) Is 1.50, each catalytic activity index is better than that of a commercial Pt/C catalyst, and the catalyst has potential application prospect.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a Pt-CuGaO for a direct methanol fuel cell anode 2 a/C composite catalyst and preparation thereof, in particular to a Pt-CuGaO for a direct methanol fuel cell anode based on a copper-gallium oxide carrier 2 a/C composite catalyst and a preparation method thereof.
Background
Methanol is used as a carrier of carbon and hydrogen energy, and has basic physical properties of liquid state at normal temperature and normal pressure, so that the preparation, storage, transportation and energy form conversion are safer and more convenient, and the methanol attracts wide attention. Electrochemical methanol oxidation reaction is used as anode reaction of direct methanol fuel cell, and is a key route of renewable energy technology. However, significant challenges remain in preparing low cost, carbon monoxide poisoning resistant and stable electrocatalysts for direct methanol fuel cell anodes, which is also a major problem limiting the commercialization of direct methanol fuel cells. However, the current anode catalyst has the problems of high possibility of being poisoned by CO, high overpotential, poor reaction kinetics, large consumption of noble metal and the like, and the application of the direct methanol fuel cell is limited by the problems. Therefore, the development of the novel direct methanol fuel cell anode catalyst carrier is beneficial to reducing the consumption of noble metals, improving the stability and reducing the cost. Therefore, the preparation of a non-noble metal system and an oxide carrier with good stability and favorable for the uniform dispersion of noble metals on the surface has important significance for the development of efficient and reliable direct methanol fuel cells.
Compared with noble metals, the copper and gallium elements are widely distributed and have lower price. Copper gallium oxide is less studied as a support of an anode catalyst of a direct methanol fuel cell, particularly as a support of a platinum-based catalyst. And by adjusting the addition amount of a mineralizer KOH in the precursor and the proportion of copper salt and gallium salt, and adding a certain amount of surfactant by an optimized hydrothermal method, the hexagonal flaky delafossite copper-gallium oxide is obtained and used as an anode catalyst carrier, and the anti-poisoning performance, the noble metal nanoparticle dispersibility and the cycling stability of the catalyst can be remarkably improved. In addition, because gallium has strong affinity to oxygen, the delafossite copper gallium oxide carrier can also provide a large amount of oxygen adsorption species in the catalytic methanol oxidation process, so that the complete oxidation of methanol is promoted, and the catalytic dynamic performance of the catalyst is improved.
On the basis of the prior art, the invention firstly provides a novel copper gallium oxide with a delafossite structure as a direct methanol fuel cell anode catalyst carrier, can realize extremely low noble metal consumption, good stability in an acid environment and strong carbon monoxide poisoning resistance, has higher performance than the current commercial Pt/C catalyst, and has good application prospect.
Disclosure of Invention
The invention aims to provide a Pt-CuGaO for a direct methanol fuel cell anode 2 a/C composite catalyst and a preparation method thereof; used for reducing the cost of the catalyst and improving the stability, the activity and the carbon monoxide poisoning resistance of the catalyst.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a Pt-CuGaO based on a copper gallium oxide carrier 2 the/C composite catalyst is characterized in that the catalyst is CuGaO with a delafossite structure 2 The surface of the oxide carrier is loaded with nano platinum, the mass of the platinum nano particles accounts for 5-15 wt% of the total mass of the composite catalyst, and the mass of C accounts for 30-50 wt% of the total mass of the composite catalyst. C is also loaded on Pt-CuGaO 2 Oxide support surface.
As one embodiment, the platinum nanoparticles have a particle size of 5 to 10nm; the CuGaO 2 The oxide carrier is hexagonal sheet structure with particle size of 5-8 μm, and the platinum nanoparticles are uniformly dispersed in CuGaO 2 And (3) oxidizing the surface.
The invention also relates to Pt-CuGaO 2 A hydrothermal preparation method of a/C composite catalyst, the method comprising the steps of:
s1, dissolving copper nitrate and gallium nitrate by using water and ethylene glycol as solvents, adding potassium hydroxide as a mineralizer, and Cetyl Trimethyl Ammonium Bromide (CTAB) as a morphology improver and a surfactant, stirring for 0.5-2h in a water bath (stirring for 0.5-2h at a constant temperature of 0-4 ℃ to obtain blue suspension), transferring the blue suspension into a hydrothermal reaction kettle (adding a tetrafluoroethylene hydrothermal kettle inner container), and reacting for 12-24h at a temperature of 160-200 ℃ to obtain a yellow brown suspension precursor;
s2, centrifuging and separating a yellow brown suspension precursor (6000-10000 rpm at room temperature) to remove a supernatant to obtain a yellow solid,washing the obtained solid (washing with dilute hydrochloric acid, dilute ammonia water, deionized water and anhydrous ethanol for 1-3 times), removing impurities, and vacuum drying (oven drying at 65-80 deg.C for 12-24 hr); adding water and glycol as mixed solvent, and reducing chloroplatinic acid by using polyalcohol thermal method to obtain copper-iron-ore copper-gallium oxide Pt-Cu GaO loaded with nano platinum 2 ；
S3, carrying out microwave batch reaction on the Pt-CuGaO 2 Loading the Pt powder and carbon powder by the mass ratio of 1:1-3:1 to obtain the Pt-CuGaO 2 a/C composite catalyst.
Compared with the traditional impregnation method and coprecipitation method, the optimized hydrothermal method adopted by the invention has the advantages that the obtained crystal phase is purer, the reaction method is more environment-friendly, the particle size distribution of the obtained hexagonal sheet structure is uniform, and the specific surface area and the stability are increased. The prepared copper gallium oxide Pt-CuGaO 2 The structure is a delafossite structure, and compared with other structures such as brucite and spinel structures, the stability and activity are better. Meanwhile, the special layered structure of the delafossite oxide can expose more gallium atoms, provide more methanol adsorption sites and active hydroxide intermediates, and promote the anode catalysis process.
As an embodiment, in the reaction system in the step S1, potassium hydroxide is prepared into a 2M solution, and the solution is dropwise added into a solution of copper nitrate and gallium nitrate while stirring, so that the stability of the suspension is ensured.
As an embodiment, naOH is also added as a mineralizer to the hot polyol reduction chloroplatinic acid system in step S2. CuGaO per 100mg of delafossite 2 Oxide support corresponding to 26.67-40mg H 2 PtCl 6 ·6H 2 O and 160mg NaOH.
As an embodiment, in step S3, pt-CuGaO is added 2 Ultrasonically dispersing the carbon powder and 1:1-3:1 in isopropanol according to the mass ratio, drying for 10-14h at the temperature of 60-80 ℃, and carrying out microwave batch reaction.
As an embodiment, in step S1, the molar ratio of potassium hydroxide to copper nitrate and gallium nitrate is 4.
As an embodiment, in step S1, the concentration of CTAB in the mixture is 0.01-0.1mol/L.
As an embodiment, in step S1, the temperature of the water bath is 0 to 4 ℃.
As an embodiment, in the step S2, the reaction temperature corresponding to the thermal reduction of the polyol is 120-160 ℃, and the reaction time is 8-12h.
As an embodiment, in step S3, the microwave batch reaction method is to heat for 10-20S at 2000-3000MHz under 500-1000W for 60-120S intermittently, and six cycles are performed. Preferably, heating is carried out at 2000MHz and 500-700W for 10-20s, and the heating is carried out intermittently for 60-120s for six cycles.
In some embodiments, the preparation steps are as follows:
1) Copper nitrate, gallium nitrate and 0.015mol/L CATB at a molar ratio of 1:1 were dissolved in 70mL deionized water: dissolving in 1:1 (volume ratio) glycol mixed solvent under stirring in water bath at 4 ℃;
2) Adding a certain amount of potassium hydroxide into the solution in the step 1) and stirring until a light blue turbid liquid is formed;
3) Transferring the solution in the step 2) to a hydrothermal reaction kettle, and heating and stirring at 160-200 ℃ for 12-24h;
4) Pouring the yellow brown suspension obtained in the step 3) into a 50mL round-bottom centrifuge tube, centrifuging at room temperature at 6000-10000rpm to remove supernatant to obtain yellow solid, washing the obtained solid with dilute hydrochloric acid, dilute ammonia water, deionized water and absolute ethyl alcohol for 1-3 times to remove impurities; drying the washed substances in a vacuum drying oven at 65-80 ℃ for 12-24h to obtain yellow solid copper gallium oxide;
5) Weighing 100mg of the above delafossite oxide, and ultrasonically dispersing in 60mL of deionized water: to a mixture of ethylene glycol 1:1 (by volume) was added 26.67mg of H 2 PtCl 6 ·6H 2 Mixing O and 160mg of mineralizer NaOH uniformly, transferring the mixture into a 100mL hydrothermal reaction kettle, reacting for 10 hours at 120 ℃, cooling the product to room temperature, centrifuging at 6000 rpm, washing with dilute hydrochloric acid, deionized water and absolute ethyl alcohol for 2 times respectively, and drying in a vacuum drying oven at 70 ℃ to obtain the platinum-loaded copper gallium oxide Pt-CuGaO 2 81mg；
6) The Pt-CuGaO obtained in the step 5) is mixed 2 And equal qualityUltrasonically dispersing purchased American Cabot Vulcan XC-72 carbon powder for 1 hour in 20mL of isopropanol, drying for 12 hours in a vacuum drying oven at 70 ℃, heating the mixed powder in a microwave oven under the conditions of 2000-3000MHz and 500-1000W for six intermittent cycles, and cooling to obtain the copper-gallium oxide loaded direct methanol fuel cell composite anode electrocatalyst Pt-CuGaO 2 /C。
The invention also relates to Pt-CuGaO 2 The application of the/C composite catalyst in the anode catalyst of the direct methanol fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
1) The Pt-CuGaO based on the copper gallium oxide carrier prepared by the invention 2 the/C composite electrocatalyst is used for direct methanol fuel cell anode catalysis. Pt and CuGaO 2 The carrier has oxygen-philic gallium which can provide abundant hydroxide species and active centers on the surface of the catalyst; the obtained composite catalyst system obtains 653.4mA/mg Pt -1 Mass activity, 2.53mA/cm 2 Specific activity of 25.83m 2 (ii) electrochemical active area in g, ratio of forward peak current density to reverse peak current density (I) as an indicator of resistance to carbon monoxide poisoning f /I b ) Is 1.50, and each catalytic activity index is better than that of a commercial Pt/C catalyst.
2) The synthesis method adopted by the invention is a hydrothermal method, toxic wastes are not generated in the process, compared with a sol-gel method, an ion exchange method and a solid-phase reaction method, toxic and harmful substances are not generated in the synthesis process, the green chemical requirements are met, the obtained product has uniform particle size distribution, the platinum nanoparticle load stability is improved, meanwhile, the uniform morphology and gallium have stronger hydrophilicity, and compared with systems such as copper aluminum oxide and the like, the catalyst has higher catalytic activity and anti-poisoning performance.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows Pt-CuGaO in example 1 2 /C compositeTEM images of the electrocatalyst;
FIG. 2 is a schematic representation of CuGaO used in example 1 2 XRD pattern of (a);
FIG. 3 is a diagram of Pt-CuGaO in example 1 2 the/C composite electrocatalyst is prepared in the range of 0.5M H 2 SO 4 +1M CH 3 CV diagram of OH.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the invention.
Example 1
1) Weighing 12mmol of Cu (NO) 3 ) 2 · 3 H 2 O (2.89 g) and 12mmol Ga (NO) 3 ) 3 ·xH 2 O (1.85 g) was dissolved in 70mL deionized water: dissolving ethylene glycol 1:1 (volume ratio) in the mixed solution by stirring at 4 ℃;
2) To the solution in 1) above was added 0.1mmol (38 mg) of CTAB and stirred for 10 min;
3) Adding 2M KOH solution into the solution obtained in the step 2) to the pH value of 13, and stirring for 45 minutes to obtain a blue uniform suspension;
4) Transferring the suspension in the step 3) into a tetrafluoroethylene inner container of a 100mL hydrothermal kettle, putting the kettle into an air-blast drying oven, heating to 200 ℃, and standing for 24 hours;
5) After the reaction is finished, slowly cooling the mixture to room temperature, and centrifuging the mixture at 8000rpm to remove supernatant liquid to obtain a tan solid;
6) Washing the yellow brown solid obtained in the step 5) with 1M dilute hydrochloric acid, 1M dilute ammonia water, deionized water and anhydrous ethanol for 2 times, and drying in a vacuum drying oven at 70 deg.C for 18 hr to obtain light yellow solid CuGaO 2 1.28g；
8) Weighing 100mg of the copper-gallium-copper-iron ore oxide, and ultrasonically dispersing in 60mL of deionized water: to a mixture of ethylene glycol 1:1 (by volume) was added 26.67mg of H 2 PtCl 6 ·6H 2 Mixing O and 160mg NaOH, transferring into a 100mL hydrothermal reaction kettle, reacting for 10 hours at 120 ℃, cooling the product to room temperature, centrifuging at 6000 rpm, washing with dilute hydrochloric acid, deionized water and absolute ethyl alcohol for 2 times respectively, and drying at 70 ℃ in a vacuum drying oven to obtain the platinum-loaded copper gallium oxide Pt-CuGaO 2 81mg；
9) The Pt-CuGaO obtained in the step 8) is mixed 2 Ultrasonically dispersing the mixed powder with equal mass of purchased American Cabot Vulcan XC-72 carbon powder for 1 hour in 20mL of isopropanol, drying the mixed powder in a vacuum drying oven at 70 ℃, heating the mixed powder in a microwave oven under the conditions of 2000MHz and 700W for 20s, intermittently performing 60s, performing six cycles, and cooling to obtain the copper-gallium oxide loaded direct methanol fuel cell composite anode electrocatalyst Pt-CuGaO 2 /C。
The morphology analysis of the Pt-CuGaO2/C obtained in example 1 was performed by a Transmission Electron Microscope (TEM), and the test results are shown in FIG. 1. It can be seen from FIG. 1 that the oxide carrier has a uniform hexagonal sheet structure.
The CuGaO obtained in example 1 was subjected to X-ray diffractometry (XRD) 2 The morphology analysis is carried out, the test result is shown in figure 2, and the test result is CuGaO shown in figure 2 2 Pure phase.
Electrochemical cyclic voltammetry was used to measure the methanol catalytic activity of the prepared anodic oxidant, carried out in an electrochemical workstation (CHI 760e, shanghai Chenhua) using a conventional three-electrode system, with a graphite sheet as the counter electrode, a Standard Calomel Electrode (SCE) as the reference electrode, and a catalyst-coated glassy carbon electrode (3 mm diameter) as the working electrode.
The catalyst slurry is prepared from 10mgPt-CuGaO 2 the/C was dispersed in 2mL of water containing 0.5wt% of Nafion 40. Mu.L, and sonicated for 30min to form a uniform suspension. 10 μ L of catalyst ink was dropped on the glassy carbon electrode whose surface was polished and dried, to serve as a working electrode.
1.0mol/L CH under an argon atmosphere in cyclic voltammetry 3 OH/0.5mol/L H 2 SO 4 The results of cyclic voltammetry tests performed in aqueous solution at a scan rate of 50mV/s are shown in FIG. 3. It can be seen from FIG. 3 that the mass activity density is much higher than that of the commercial Pt/C catalystAn oxidizing agent.
Comparative example 1
1) Weighing 12mmol of Cu (NO) 3 ) 2 · 3 H 2 O (2.89 g) and 12mmol Ga (NO) 3 ) 3 ·xH 2 O (1.85 g) was dissolved in 70mL deionized water: dissolving ethylene glycol 1:1 (volume ratio) in the mixed solution by stirring at 4 ℃;
2) To the solution in 1) above was added 0.1mmol (38 mg) of CTAB and stirred for 10 min;
3) Adding 2M KOH solution into the solution in the step 2) to reach the pH value of 13, and stirring for 45 minutes to obtain a blue uniform suspension;
4) Transferring the suspension in the step 3) into a tetrafluoroethylene inner container of a 100mL hydrothermal kettle, putting the kettle into an air-blast drying oven, heating to 200 ℃, and standing for 24 hours;
5) After the reaction is finished, slowly cooling the mixture to room temperature, and centrifuging the mixture at 8000rpm to remove supernatant liquid to obtain a tan solid;
6) Washing the yellow brown solid obtained in the step 5) with 1M dilute hydrochloric acid, 1M dilute ammonia water, deionized water and anhydrous ethanol for 2 times, and drying in a vacuum drying oven at 70 deg.C for 18 hr to obtain light yellow solid CuGaO 2 1.28g；
7) Weighing 100mg of the copper-gallium-delafossite oxide, and ultrasonically dispersing in 60mL of deionized water: to a mixture of ethylene glycol 1:1 (by volume) was added 26.67mg of H 2 PtCl 6 ·6H 2 Mixing O and 160mg NaOH, transferring into a 100mL hydrothermal reaction kettle, reacting for 10 hours at 120 ℃, cooling the product to room temperature, centrifuging at 6000 rpm, washing with dilute hydrochloric acid, deionized water and absolute ethyl alcohol for 2 times respectively, and drying at 70 ℃ in a vacuum drying oven to obtain the platinum-loaded copper gallium oxide Pt-CuGaO 2 87mg。
The obtained catalyst was subjected to electrochemical tests, and no methanol oxidation current was obtained due to the high base resistance.
Comparative example 2
1) Weighing 12mmol of Cu (NO) 3 ) 2 · 3 H 2 O (2.89 g) and 12mmol Ga (NO) 3 ) 3 ·xH 2 O (1.85 g) was dissolved in 70mL deionized water: ethylene glycol 1:1 (volume ratio)) Stirring the mixed solution at 4 ℃ until the mixed solution is dissolved;
2) To the solution in 1) above was added 0.1mmol (38 mg) of CTAB and stirred for 10 min;
3) Adding 2M KOH solution into the solution obtained in the step 2) to the pH value of 13, and stirring for 45 minutes to obtain a blue uniform suspension;
4) Transferring the suspension in the step 3) into a tetrafluoroethylene inner container of a 100mL hydrothermal kettle, putting the kettle into an air-blast drying oven, heating to 200 ℃, and standing for 24 hours;
5) After the reaction is finished, slowly cooling the mixture to room temperature, and centrifuging the mixture at 8000rpm to remove supernatant liquid to obtain a tan solid;
6) Washing the yellow brown solid obtained in the step 5) with 1M dilute hydrochloric acid, 1M dilute ammonia water, deionized water and anhydrous ethanol for 2 times, and drying in a vacuum drying oven at 70 deg.C for 18 hr to obtain yellow solid CuGaO 2 1.28g；
8) Weighing 100mg of the copper-gallium-copper-iron ore oxide and 100mg of XC-72 carbon powder, and ultrasonically dispersing in 60mL of deionized water: to a mixture of ethylene glycol 1:1 (by volume) was added 26.67mg of H 2 PtCl 6 ·6H 2 Mixing O and 160mg NaOH, transferring into a 100mL hydrothermal reaction kettle, reacting for 10 hours at 120 ℃, cooling the product to room temperature, centrifuging at 6000 rpm, washing with dilute hydrochloric acid, deionized water and absolute ethyl alcohol for 2 times respectively, and drying in a vacuum drying oven at 70 ℃ to obtain the platinum and carbon loaded copper-gallium oxide Pt/C-CuGaO 2 177mg。
The obtained catalyst is tested, and a large amount of platinum nano-particles are directly loaded on carbon powder due to a one-pot method, so that the advantages of the copper-gallium-delafossite oxide carrier are not exerted, and the methanol oxidation quality activity and the anti-toxicity performance of the catalyst are weaker than those of Pt-CuGaO2/C and higher than those of commercial Pt/C.
The above description has fully demonstrated the Pt-CuGaO to which the present invention relates 2 ABO as the anode electrocatalyst of the/C composite direct methanol fuel cell 2 The delafossite copper gallium oxide with the structure is used as a carrier of nano platinum, and the load of the nano platinum is 5wt%; during preparation, the copper-gallium oxide carrier is synthesized by a hydrothermal method, and nano platinum and micro platinum are reduced by a polyalcohol thermal methodLoading carbon powder by the wave batch reaction method to obtain the high-efficiency and stable Pt-CuGaO 2 5wt.% of the catalyst gave 653.4mA/mg Pt -1 Mass activity, 2.53mA/cm 2 Specific activity of 25.83m 2 (ii) electrochemical active area in g, which is indicative of the ratio of the forward peak current density to the reverse peak current density (I) of the carbon monoxide poisoning resistance f /I b ) Is 1.50, each catalytic activity index is better than that of a commercial Pt/C catalyst, and the catalyst has potential application prospect.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. Pt-CuGaO based on copper gallium oxide carrier 2 the/C composite catalyst is characterized in that the catalyst is CuGaO with a delafossite structure 2 The surface of the oxide carrier is loaded with nano platinum, the mass of the platinum nano particles accounts for 5-15 wt% of the total mass of the composite catalyst, and the mass of C accounts for 30-50% of the total mass of the composite catalyst.
2. The Pt-CuGaO of claim 1 2 the/C composite catalyst is characterized in that the particle size of the platinum nano particles is 5-10nm; the CuGaO 2 The oxide carrier is hexagonal sheet structure with particle size of 5-8 μm, and the platinum nanoparticles are uniformly dispersed in CuGaO 2 Oxide surface.
3. The Pt-CuGaO of claim 1 or 2 2 The preparation method of the/C composite catalyst is characterized by comprising the following steps:
s1, dissolving copper nitrate and gallium nitrate by using water and ethylene glycol as solvents, adding potassium hydroxide as a mineralizer, and cetyl trimethyl ammonium bromide as a surfactant and a morphology control agent, stirring for 0.5-2h in a water bath, transferring into a hydrothermal reaction kettle, and reacting for 12-24h at 160-200 ℃ to obtain a tawny suspension precursor;
s2, centrifugally separating the yellow brown suspension precursor to remove supernatant liquid to obtain yellow solid, washing the obtained solid, removing impurities, and then drying in vacuum to obtain yellow solid copper gallium oxide; adding water and glycol as a mixed solvent, and reducing chloroplatinic acid by a polyol thermal method to obtain the nano-platinum-loaded delafossite copper-gallium oxide Pt-CuGaO 2 ；
S3, carrying out microwave batch reaction on the Pt-CuGaO 2 Loading the Pt powder and carbon powder by the mass ratio of 1:1-3:1 to obtain the Pt-CuGaO 2 a/C composite catalyst.
4. The method according to claim 3, wherein in step S1, the molar ratio of gallium nitrate to copper nitrate is 1:1, and potassium hydroxide is added to adjust the pH to 11.
5. The method according to claim 3, wherein in step S1, the concentration of cetyltrimethylammonium bromide in the mixture is 0.01-0.1mol/L.
6. The method according to claim 3, wherein the temperature of the water bath in step S1 is 0 to 4 ℃.
7. The method according to claim 3, wherein the centrifugation is carried out at 6000 to 10000rpm at room temperature and the vacuum drying is carried out at 65 to 80 ℃ for 12 to 24 hours in step S2.
8. The method according to claim 3, wherein in step S2, the reaction temperature for the thermal reduction of the polyol is 120-160 ℃ and the reaction time is 8-12h.
9. The method according to claim 3, wherein the microwave batch reaction method is carried out for six cycles by heating at 2000MHz at 500-700W for 10-20S and for 60-120S.
10. The Pt-CuGaO of claim 1 or 2 2 /C hybrid catalyst, or Pt-CuGaO obtainable according to the process of any one of claims 3 to 9 2 The application of the/C composite catalyst in the anode catalyst of the direct methanol fuel cell.
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