CN115000434B - Direct ethanol fuel cell electrocatalyst with functional carrier and preparation method thereof - Google Patents

Direct ethanol fuel cell electrocatalyst with functional carrier and preparation method thereof Download PDF

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CN115000434B
CN115000434B CN202210446800.0A CN202210446800A CN115000434B CN 115000434 B CN115000434 B CN 115000434B CN 202210446800 A CN202210446800 A CN 202210446800A CN 115000434 B CN115000434 B CN 115000434B
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alti
altio
fuel cell
functional carrier
functional
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CN115000434A (en
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陈腾
胡建强
马军
郭力
徐新
杨士钊
谢凤
季峰
王玉梅
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Air Force Logistics University Of Pla
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H01M8/1013—Other direct alcohol fuel cells [DAFC]
    • 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

An electrocatalyst for direct alcohol fuel cell with functional carrier and its preparing process x AlTi@AlTiO of oxide layer x Functional carrier, alTi@AlTiO x The functional carrier is in a three-dimensional porous sponge shape, and nano platinum particles which are uniformly distributed are also loaded on the surface of the functional carrier. In the process of catalytic reaction, the electrocatalyst of the invention is prepared from AlTi@AlTiO x AlTiO formed on the surface of functional support x The oxidation layer is used as a first active center to dehydrate ethanol molecules, and then formed ethylene is transferred to a second active center formed by nano platinum particles to be oxidized on the surface of metal Pt, so that C-C fracture is promoted, and the ethanol oxidation rate is improved; and AlTiO x The oxide layer has acid corrosion resistance so as to have excellent stability.

Description

Direct ethanol fuel cell electrocatalyst with functional carrier and preparation method thereof
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a direct ethanol fuel cell electrocatalyst with a functional carrier and a preparation method thereof.
Background
The direct ethanol fuel cell (also called DEFCs) can be well adapted to the fields of power generation, fixation, energy source, environmental requirements and the like which are urgently needed at present due to the characteristics of high efficiency, no pollution and environmental friendliness, and has wide application prospect. At present, in the process of electrocatalytic oxidation of ethanol anode, problems still exist, such as slow reaction kinetics, unavoidable poisoning, incomplete oxidation behavior and the like, which seriously inhibit the large-scale application of DEFCs.
The ethanol electrooxidation reaction (also known as EOR) follows a dual-path reaction mechanism (i.e., the C1 path and the C2 path). Complete oxidation of ethanol to CO in the C1 path 2 The product, transfer 12 electrons; under the C2 pathway, ethanol oxidizes to acetic acid product, transferring 4 electrons. Clearly, increasing the faraday efficiency of the C1 path is of great importance for improving the efficiency of direct ethanol fuel cells, but this is also a long-felt difficulty. During the ethanol electrooxidation reaction of acidic solutions, the C2 pathway (i.e., the incomplete oxidation mechanism) dominates over the C1 pathway (the complete oxidation mechanism). Thus, promoting the C-C cleavage of ethanol molecules and improving the anti-toxin capability of ethanol molecules are two key problems in designing an electrocatalyst for the efficient ethanol electrooxidation reaction. The most widely used catalysts at present are the traditional commercial Pt/C catalysts, which have great disadvantages in terms of suppression of CO poisoning and promotion of c—c bond cleavage.
In recent years, a great deal of research is being conducted at home and abroad on improving the electrocatalytic reaction rate of ethanol molecules and the antitoxic capability and stability of the catalyst. The name of Construction of Pd-Zn dual sites to enhance the performance for ethanol electro-oxidation reaction reports that construction of Pd-Zn double sites with good exposure and uniformity can significantly improve the electrooxidation efficiency of ethanol. By controlling the synthesis method, pd-Zn double centers are respectively obtained on intermetallic compound PdZn nano particles, pd-Pd centers are obtained on the Pd nano particles, and Pd-Pd centers and single Pd centers are respectively obtained on the same N-doped carbon-coated ZnO carrier. The alcohol electrooxidative activity of Pd-Zn double centers is much higher than Pd-Pd centers and Pd centers alone, about 24 times higher than commercial Pd/C. Named as Enhancing C-C Bond Scission for Efficient Ethanol Oxidation using PtIr Nanocube ElectrocThe paper by atalysts was based on the Langmuir-Hinshelwood mechanism, which constructed Rh-Bi (OH) 3 The double-function catalytic interface realizes the effective breaking of ethanol C-C bond and the rapid oxidation of strong adsorption C1 species, and remarkably improves the activity, stability and carbon dioxide selectivity of EOR under alkaline conditions.
Therefore, the catalyst structure is reasonably designed to promote the C-C bond to break and accelerate the oxidation of the strongly adsorbed C1 species, and is an effective method for obtaining the high-activity ethanol electro-oxidation catalyst. However, the prior art has a great technical bottleneck, resulting in unsatisfactory performance or non-large-scale production. Therefore, designing a catalyst which is low in cost, easy to operate, high in performance and capable of being produced in large scale is still an important subject of current research.
Disclosure of Invention
Based on the above, the invention provides a direct ethanol fuel cell electrocatalyst with a functional carrier and a preparation method thereof, so as to solve the technical problems that the performance of the catalyst in the prior art is not ideal or the catalyst cannot be produced in a large scale.
To achieve the above object, the present invention provides a direct ethanol fuel cell electrocatalyst with a functional support comprising AlTiO formed by surface oxidation x AlTi@AlTiO of oxide layer x Functional carrier, the AlTi@AlTiO x The functional carrier is in a three-dimensional porous sponge shape, and nano platinum particles which are uniformly distributed are also loaded on the surface of the functional carrier.
As a further preferable technical scheme of the invention, the metal Pt in the nano platinum particles is in AlTi@AlTiO x The loading capacity on the functional carrier is 1-40%.
As a further preferable technical scheme of the invention, the diameter of the nano platinum particles is 1nm-1000nm.
As a further preferable embodiment of the present invention, the AlTiO x The thickness of the oxide layer is 0.1nm-2nm.
According to another aspect of the present invention, there is provided a method for preparing the electrocatalyst for a direct ethanol fuel cell with a functional support according to any one of the preceding claims, comprising the steps of:
1) Soaking three-dimensional porous spongy AlTi alloy in alkaline solution, and then soaking in acidic solution to obtain a surface-treated AlTi alloy carrier, wherein stirring is needed in the soaking process;
2) Soaking the AlTi alloy carrier subjected to surface treatment in a platinum metal precursor solution, and carrying out electrochemical deposition and drying to obtain a Pt/AlTi intermediate with uniformly distributed nano platinum particles loaded on the surface;
3) Placing Pt/AlTi intermediate in an atmosphere containing oxygen, heating to oxidize the surface of AlTi alloy carrier to form AlTiO x An oxide layer to obtain a direct ethanol fuel cell electrocatalyst with a functional carrier, which is also called Pt/AlTi@AlTiO x A catalyst.
As a further preferred embodiment of the present invention, the three-dimensional porous sponge-like AlTi alloy in step 1) is prepared by 3D printing, and its structure is a three-dimensional porous sponge-like cylinder.
As a further preferable technical scheme of the invention, in the step 1), the alkaline solution is potassium hydroxide, sodium hydroxide or a mixed solution of the potassium hydroxide and the sodium hydroxide with the concentration of 0.5mol/L to 12mol/L, and the soaking time of the three-dimensional porous spongy AlTi alloy in the alkaline solution is 0.5h to 12h; the acidic solution is hydrochloric acid or sulfuric acid solution with the concentration of 0.1mol/L-6mol/L, and the soaking time of the three-dimensional porous spongy AlTi alloy in the acidic solution is 0.5h-12h.
In the step 2), a platinum metal precursor solution comprises a platinum metal precursor and deionized water in a mass ratio of 1:1-50, wherein the platinum metal precursor is chloroplatinic acid, platinum acetylacetonate or chloroplatinic acid salt.
As a further preferable embodiment of the present invention, in step 2), the electrochemical deposition is one of cyclic voltammetry, potentiostatic deposition, galvanostatic deposition, and pulsed deposition.
In the step 3), the gas used in the atmosphere containing oxygen is air or a mixed gas of oxygen and inert gas with the volume fraction of 1% -100%; the inert gas is nitrogen, argon or helium; the heating temperature is 20-200 ℃ and the heating time is 0.2-12h.
The direct ethanol fuel cell electrocatalyst with the functional carrier and the preparation method thereof can achieve the following beneficial effects by adopting the technical scheme:
1) The invention relates to a direct ethanol fuel cell electrocatalyst with a functional carrier, which is prepared from AlTi@AlTiO in the catalytic reaction process x AlTiO formed on the surface of functional support x The oxidation layer is used as a first active center to dehydrate ethanol molecules, formed ethylene is transferred to a second active center formed by nano platinum particles to be oxidized on the surface of metal Pt, and C-C fracture is promoted, so that the ethanol oxidation rate is improved;
2) The invention provides a direct ethanol fuel cell electrocatalyst with a functional carrier, which is prepared by adopting AlTi@AlTiO x AlTiO formed on the surface of the carrier x The oxide layer has outstanding acid corrosion resistance, thereby leading Pt/AlTi@AlTiO x The catalyst exhibits excellent stability;
3) The direct ethanol fuel cell electrocatalyst with the functional carrier provided by the invention has the advantages of low loading capacity, high utilization rate of noble metal platinum, low cost, easiness in operation and the like, can be produced in a large scale, and can show excellent catalytic activity and stability in an electrocatalytic ethanol oxidation reaction;
4) The preparation method of the direct ethanol fuel cell electrocatalyst with the functional carrier provided by the invention is simple to operate, the loading amount of the metal platinum is controllable, and the formed nano platinum particles can be uniformly distributed and loaded on AlTi@AlTiO x A functional carrier surface.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 shows Pt/AlTi@AlTiO according to the invention x Schematic diagram of catalytic ethanol oxidation principle by using catalyst;
FIG. 2 shows Pt/AlTi@AlTiO according to the invention x Macroscopic photographs of the catalyst;
FIG. 3 shows the Pt/AlTi@AlTiO obtained in example 1 x Catalyst sweep at 200-fold magnificationDrawing an electron microscope photo;
FIG. 4 shows the Pt/AlTi@AlTiO obtained in example 1 x Scanning electron microscope pictures of the catalyst amplified 1000 times;
FIG. 5 shows the Pt/AlTi@AlTiO obtained in example 1 x Scanning electron microscope pictures of the catalyst after a period of catalytic reaction;
FIG. 6 shows the Pt/AlTi@AlTiO obtained in example 1 x Comparison graphs of catalytic activity of the catalyst and the comparative sample Pt/C catalyst;
FIG. 7 shows the Pt/AlTi@AlTiO obtained in example 1 x Comparison of catalytic stability of the catalyst and the comparative sample Pt/C catalyst.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The invention will be further described with reference to the drawings and detailed description. The terms such as "upper", "lower", "left", "right", "middle" and "a" in the preferred embodiments are merely descriptive, but are not intended to limit the scope of the invention, as the relative relationship changes or modifications may be otherwise deemed to be within the scope of the invention without substantial modification to the technical context.
The invention provides a direct ethanol fuel cell electrocatalyst with a functional carrier, which is also called Pt/AlTi@AlTiO x Electrocatalyst comprising three-dimensional porous sponge AlTi@AlTiO x Functional carrier, alTi@AlTiO x The surface of the functional carrier is oxidized to form AlTiO with the thickness of 0.1nm-2nm x An oxide layer and nano platinum particles with diameters of 1nm-1000nm and uniform distribution are loaded, wherein the metal Pt is prepared from AlTi@AlTiO x The loading capacity on the functional carrier is 1-40%, and AlTi@AlTiO is defined x The functional carrier is a first active center, and the nano platinum particles are a second active center.
The electro-catalyst of the invention is shown in figure 1 in the process of catalyzing ethanol electro-oxidation, wherein ethanol molecules are AlTiO at the first active center first x Surface dehydration of the oxide layer, the ethylene formed is transferred to a second livingContinuing oxidation of the surface of the nano platinum particles in the sexual center; at the same time, alTi@AlTiO x the-OH formed on the surface of the functional carrier can promote the desorption of CO in an adsorption state from the surface of the metal Pt, so that the chemical reaction rate of the electrooxidation of the ethanol is improved; and AlTiO formed on the surface of the carrier x The oxide layer has outstanding acid corrosion resistance, so that Pt/AlTi@AlTiO x The catalyst shows excellent ethanol oxidation activity and stability.
In one embodiment, the macroscopic result of the Pt/AlTi@AlTiOx catalyst is shown in FIG. 2, and it can be seen from FIG. 2 that the monolithic catalyst is a three-dimensional porous sponge-like cylinder with a length of about 4 cm and a diameter of about 2 cm, and AlTi@AlTiO is added due to the three-dimensional porous sponge-like structure x The specific surface area of the functional carrier is beneficial to deposition of Pt catalytic sites, and meanwhile is beneficial to rapid transmission of reactants and products, so that the diffusion and transmission resistance of the reactants are reduced.
In order to enable those skilled in the art to further understand the technical scheme of the present invention, the technical scheme of the present invention is further described in detail through specific embodiments.
Example 1
(1) Preparation of AlTi alloy support
And (3) soaking the three-dimensional porous spongy AlTi alloy in a 6mol/L potassium hydroxide solution, stirring for 5 hours, rapidly transferring to a 1mol/L hydrochloric acid solution, and continuously soaking for 2 hours under stirring to remove a part of oxide layer formed on the surface of the AlTi alloy, thereby obtaining the surface-treated AlTi alloy carrier.
(2) Preparation of Pt/AlTi intermediates
Weighing 0.2g of chloroplatinic acid according to the metal Pt carrying amount of 10%, and dissolving the chloroplatinic acid in deionized water according to the mass ratio of the chloroplatinic acid to the deionized water of 1:10 to obtain an aqueous solution of the chloroplatinic acid; immersing all the surface-treated AlTi alloy carriers into a chloroplatinic acid aqueous solution for 30 minutes; taking Ag/AgCl as a reference electrode, taking Pt wires as a counter electrode, taking an AlTi alloy carrier as a working electrode, and carrying out electrochemical deposition by a cyclic voltammetry in a potential range of-0.35-0.25V (relative to the Ag/AgCl electrode), wherein the scanning speed is 10mv/s, and the scanning circle number is 2000; and (5) placing the electrodeposited sample into a drying oven to be dried at 50 ℃ to obtain the Pt/AlTi intermediate.
(3)Pt/AlTi@AlTiO x Preparation of the catalyst
Placing Pt/AlTi intermediate in oxygen/nitrogen mixed gas with volume fraction of 20%, heating at 80deg.C for 2 hr to oxidize AlTi alloy carrier surface to form AlTiO x Oxide layer to obtain electrocatalyst, i.e. Pt/AlTi@AlTiO x A catalyst.
To further explore the Pt/AlTi@AlTiO of the present invention x The performance of the catalyst was tested as follows:
(1) SEM (scanning electron microscope) test
Pt/AlTi@AlTiO prepared in step (3) of the embodiment x The catalysts were tested using a scanning electron microscope at different magnifications and the results correspond to those shown in FIGS. 3 and 4, and in addition, for Pt/AlTi@AlTiO x The catalyst was subjected to stability test using a scanning electron microscope, and the results thereof correspond to those shown in fig. 5.
(2)Pt/AlTi@AlTiO x Catalytic performance comparison test of catalyst and Pt/C catalyst for catalyzing ethanol oxidation reaction
The preparation method of the catalyst takes the existing commercial Pt/C catalyst as a comparison sample and comprises the following steps: 5 mg of Pt/C is mixed with 970 microliters of isopropanol and 30 microliters of Nafion film solution (mass fraction 5% of DuPont), after ultrasonic oscillation is carried out for 40 minutes and dispersion is uniform, 5 microliters of Pt/C is sucked by a microsyringe and uniformly coated on a glassy carbon rotary ring disk electrode, and the mixture is dried in air for 10 minutes, so that the Pt/C electrocatalyst is obtained. Pt/AlTi@AlTiO x The catalysts and Pt/C electrocatalysts were tested as working electrodes as follows:
placing a working electrode at 0.1mol/L HClO 4 And 2mol/L ethanol mixed electrolyte, a three-electrode system is adopted, a working electrode is used as a test sample, an Ag/AgCl electrode is used as a reference electrode, pt wire is used as an auxiliary electrode, a cyclic voltammogram is recorded on an electrochemical workstation (CHI 660d, shanghai Chen Hua instrument Co.), the scanning speed is 20mv/s, the scanning range is 0.38-1.18V (relative to a standard hydrogen electrode), and the test result corresponds to that shown in FIG. 6A curve.
(3)Pt/AlTi@AlTiO x Stability test of catalyst and Pt/C catalyst
Test operation the test conditions of the above test (2), i.e. the current-time curve of the catalyst was tested at 1.0V (relative to a standard hydrogen electrode) using potentiostatic method under a three-electrode system, the test results corresponding to the curve in fig. 7.
The test results were analyzed as follows:
as can be seen from the scanning electron microscope pictures with different magnifications in FIG. 3 and FIG. 4, platinum particles with the particle size of about 20-500 nanometers are uniformly distributed in AlTi@AlTiO x The surface of the functional carrier proves the feasibility of preparing the Pt/AlTi@AlTiOx catalyst by a potential deposition method, and the uniform distribution of the active site nano platinum particles is beneficial to the ethanol oxidation reaction.
As can be seen from the sem pictures of the samples after the stability test of fig. 5, the structure of the spot catalyst was not changed at all after the lapse of 10 hours of catalytic reaction, and it was confirmed that the AlTiOx oxide layer formed on the surface of the alti@altiox support had outstanding acid corrosion resistance.
From FIGS. 6 and 7, it can be seen that Pt/AlTi@AlTiO prepared by the method of the invention of the present patent x Catalyst Pt/alti@altio with a platinum loading lower than that of the existing commercial Pt/C catalyst (20 wt.%) x The catalytic activity and stability of the catalyst are obviously improved compared with the comparative sample Pt/C catalyst, which shows that AlTi@AlTiO x Dehydration of ethanol by functional carrier and AlTi@AlTiO x the-OH formed on the surface of the functional carrier can effectively optimize the oxidation reaction path of the ethanol on the surface of the catalyst and promote the desorption of CO in an adsorption state from the Pt surface, so that the chemical reaction rate of the electrooxidation of the ethanol is improved; alTiO formed on the surface of the carrier x The oxide layer has outstanding acid corrosion resistance, and the overall stability of the catalyst is greatly improved.
Example 2
(1) Preparation of AlTi alloy support
And (3) placing the three-dimensional porous spongy AlTi alloy in a 6mol/L potassium hydroxide solution, stirring for 5 hours, quickly transferring to a 1mol/L hydrochloric acid solution, and soaking for 2 hours under stirring to remove a part of oxide layer formed on the surface of the AlTi alloy, thereby obtaining the surface-treated AlTi alloy carrier.
(2) Preparation of Pt/AlTi intermediates
Weighing 0.11g of ammonium chloroplatinate according to the metal Pt loading amount of 5%, and dissolving to obtain an aqueous solution of the ammonium chloroplatinate according to the mass ratio of the ammonium chloroplatinate to deionized water of 1:5; immersing the surface-treated AlTi alloy carrier into an ammonium chloroplatinate aqueous solution for 20 minutes; taking Ag/AgCl as a reference electrode, taking Pt wires as a counter electrode, taking an AlTi alloy carrier as a working electrode, and carrying out electrochemical deposition by a constant potential deposition method under the potential of 0.1V (relative to the Ag/AgCl electrode), wherein the deposition time is 20 minutes; and (3) placing the electrodeposited sample into a vacuum drying oven to be dried at 60 ℃ to obtain the Pt/AlTi intermediate.
(3)Pt/AlTi@AlTiO x Preparation of the catalyst
Placing the Pt/AlTi intermediate in a blast drying oven for heating at 60 ℃ for 5 hours to oxidize the surface of the AlTi alloy carrier to form AlTiO x Oxide layer to obtain electrocatalyst, i.e. Pt/AlTi@AlTiO x A catalyst.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.

Claims (9)

1. A preparation method of a direct ethanol fuel cell electrocatalyst with a functional carrier is characterized in that the direct ethanol fuel cell electrocatalyst with the functional carrier comprises the steps of oxidizing the surface to form AlTiO x AlTi@AlTiO of oxide layer x Functional carrier, the AlTi@AlTiO x The functional carrier is in a three-dimensional porous sponge shape, and nano platinum particles which are uniformly distributed are also loaded on the surface of the functional carrier;
the preparation method of the direct ethanol fuel cell electrocatalyst with the functional carrier comprises the following steps:
1) Soaking three-dimensional porous spongy AlTi alloy in alkaline solution, and then soaking in acidic solution to obtain a surface-treated AlTi alloy carrier, wherein stirring is needed in the soaking process;
2) Soaking the AlTi alloy carrier subjected to surface treatment in a platinum metal precursor solution, and carrying out electrochemical deposition and drying to obtain a Pt/AlTi intermediate with uniformly distributed nano platinum particles loaded on the surface;
3) Heating the Pt/AlTi intermediate in an atmosphere containing oxygen to oxidize the surface of the AlTi alloy to form AlTiO x And oxidizing the layer to obtain the direct ethanol fuel cell electrocatalyst with the functional carrier.
2. The method for preparing the direct ethanol fuel cell electrocatalyst with the functional carrier according to claim 1, wherein the metallic Pt in the nano platinum particles is represented by alti@altio x The loading capacity on the functional carrier is 1-40%.
3. The method for preparing a direct ethanol fuel cell electrocatalyst with a functional support according to claim 1, wherein the diameter of the nano platinum particles is from 1nm to 1000nm.
4. The method for preparing a direct ethanol fuel cell electrocatalyst with a functional support according to claim 1, wherein the AlTiO x The thickness of the oxide layer is 0.1nm-2nm.
5. The method according to claim 1, wherein the three-dimensional porous sponge-like AlTi alloy in step 1) is produced by 3D printing and has a three-dimensional porous sponge-like cylinder structure.
6. The preparation method according to claim 1, wherein in the step 1), the alkaline solution is potassium hydroxide, sodium hydroxide or a mixture of the potassium hydroxide and the sodium hydroxide with the concentration of 0.5mol/L to 12mol/L, and the soaking time of the three-dimensional porous sponge-like AlTi alloy in the alkaline solution is 0.5h to 12h; the acidic solution is hydrochloric acid or sulfuric acid solution with the concentration of 0.1mol/L-6mol/L, and the soaking time of the three-dimensional porous spongy AlTi alloy in the acidic solution is 0.5h-12h.
7. The preparation method according to claim 1, wherein in the step 2), the platinum metal precursor solution comprises a platinum metal precursor and deionized water in a mass ratio of 1:1-50, and the platinum metal precursor is chloroplatinic acid, platinum acetylacetonate or chloroplatinic acid salt.
8. The method according to claim 1, wherein in step 2), the electrochemical deposition is one of cyclic voltammetry, potentiostatic deposition, galvanostatic deposition, and pulsed deposition.
9. The method for preparing the direct ethanol fuel cell electrocatalyst with the functional carrier according to claim 1, wherein in step 3), the gas used in the atmosphere containing oxygen is air or a mixed gas of oxygen and inert gas in a volume fraction of 1% to 100%; the inert gas is nitrogen, argon or helium; the heating temperature is 20-200 ℃ and the heating time is 0.2-12h.
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Publication number Priority date Publication date Assignee Title
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CN112510221A (en) * 2021-02-03 2021-03-16 南京大学 Fuel cell electrocatalyst and preparation method and application thereof
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US4499205A (en) * 1982-04-12 1985-02-12 Nissan Motor Company, Limited High activity catalyst for reforming of methanol and process of preparing same
WO2013035698A1 (en) * 2011-09-09 2013-03-14 国立大学法人山梨大学 Highly active and stable catalyst particles, electrode catalyst obtained using same, and process for producing same
CN104148060A (en) * 2014-07-14 2014-11-19 天津大学 Platinum catalyst supported on double-oxide composite carrier and preparation method and application of platinum catalyst
CN112510221A (en) * 2021-02-03 2021-03-16 南京大学 Fuel cell electrocatalyst and preparation method and application thereof
CN113262781A (en) * 2021-06-02 2021-08-17 中国华能集团清洁能源技术研究院有限公司 Metal platinum catalyst and preparation method and application thereof

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