CN114388829A - Transition metal-based catalyst for direct methanol fuel cell anode and preparation method thereof - Google Patents
Transition metal-based catalyst for direct methanol fuel cell anode and preparation method thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000000446 fuel Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 23
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 239000002135 nanosheet Substances 0.000 claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000017 hydrogel Substances 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- YLZGVPCTROQQSX-UHFFFAOYSA-N [K].[Ni](C#N)C#N Chemical compound [K].[Ni](C#N)C#N YLZGVPCTROQQSX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 239000013081 microcrystal Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000002159 nanocrystal Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000010411 electrocatalyst Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
-
- 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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]
-
- 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 belongs to the technical field of fuel cells, and particularly relates to a transition metal-based catalyst for a direct methanol fuel cell anode and a preparation method thereof. The preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode comprises the following steps: (1) preparation of Ni (OH)2Ultrathin nanosheet: (2) preparation of Pt/Ni (OH)2A composite material; (3) preparing the Pt/NiO composite nano material. The method has simple preparation process, easy operation and simple structureThe preparation requirement is low, and the catalytic activity and the conductivity of the nickel oxide can be obviously improved by only using a very small amount of Pt noble metal for doping, so that the nickel oxide has excellent electrochemical reaction activity on the anode of the methanol fuel cell.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a transition metal-based catalyst for a direct methanol fuel cell anode and a preparation method thereof.
Background
Along with the rapid development of economy, the consumption speed of primary energy in China is increased day by day, the problems of energy supply shortage, environmental pollution and liquid fuel shortage, greenhouse gas emission and clean energy supply in rural areas are also important challenges facing the energy in China, and the problems cause serious restrictions on sustainable development ways in China. Therefore, China needs to change the current energy structure situation which takes fossil energy as the leading energy source, develops new clean alternative energy, reduces the dependence on primary energy, realizes energy conservation and emission reduction, and is a potential requirement for sustainable development of economy. The fuel cell is not limited by Carnot cycle, has less energy loss, has the advantages of wide fuel source, safe fuel transportation, green and clean product and low cost, and is an environment-friendly power generation device.
Direct Methanol Fuel Cells (DMFCs) directly use an aqueous solution as well as steam methanol as a fuel supply source. The hydrogen is not required to be taken out for power generation by reforming methanol, gasoline, natural gas and the like. Compared with proton exchange membrane fuel cells, DMFC has the excellent characteristics of low-temperature electricity generation, low danger of fuel components, simple cell architecture and the like, and also has the advantages of high energy conversion efficiency, lower use temperature, zero pollution, easy transportation and storage of fuel, modular structure, flexibility, convenience and the like.
For methanol fuel cells, the performance of the catalyst used is still a major factor in determining the overall performance. Existing Pt-based catalysts, while effective for electrocatalytic activity in direct methanol fuel cells, are prohibitively expensive and have limited reserves. Therefore, a novel electrocatalyst is needed, which can effectively improve the performance of the catalyst while reducing the preparation cost of the catalyst.
Disclosure of Invention
The invention aims to provide a transition metal-based catalyst for a direct methanol fuel cell anode and a preparation method thereof, aiming at the problem of low catalytic activity of the existing direct methanol fuel cell anode catalyst. The method has the advantages of simple and easy operation preparation process, low equipment requirement, uniform distribution of superfine Pt nano-crystallites, and capability of obviously improving the catalytic activity and the conductivity of the nickel oxide by only using a very small amount of Pt noble metal for doping, thereby showing excellent electrochemical reaction activity on the anode of the methanol fuel cell.
The technical scheme of the invention is as follows: a method for preparing a transition metal-based catalyst for a direct methanol fuel cell anode, comprising the steps of:
(1) preparation of Ni (OH)2Ultrathin nanosheet: firstly, dissolving nickel chloride and potassium nickel cyanide in deionized water, uniformly stirring to obtain a mixed solution, and standing at room temperature to obtain blue mixed hydrogel; then adding a reducing agent NaBH into the mixed hydrogel4Carrying out hydrothermal reduction on the solution at a constant temperature of 60-65 ℃, cooling to room temperature, centrifuging and washing to obtain black Ni (OH)2Ultrathin nanosheets;
(2) preparation of Pt/Ni (OH)2The composite material comprises the following components: mixing the Ni (OH) obtained in the step (1)2Dispersing ultrathin nanosheets and potassium chloroplatinate in deionized water, and then adding NaBH4Treating the solution in a thermostatic water bath at 50-80 ℃ for 3-12 h, centrifuging and collecting to obtain black Pt microcrystal loaded on Ni (OH)2Pt/Ni (OH) of ultrathin nanosheets2A composite material;
(3) preparing a Pt/NiO composite nano material: the Pt/Ni (OH) obtained in the step (2)2And placing the composite material in a tubular furnace, annealing for 2-5 h at 280-380 ℃ in the air, and naturally cooling to room temperature to obtain the Pt/NiO composite nano material.
The preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode comprises the following steps of (1) preparing a transition metal-based catalyst by nickel chloride according to a molar ratio: potassium nickel cyanide is 2: 1; the deionized water is 1-100 mL.
In the preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode, the step (1) is kept stand for 6-12 hours.
In the preparation method of the transition metal-based catalyst for the anode of the direct methanol fuel cell, step (1) NaBH4The concentration of the solution is 0.1-2 g/mL, and the dosage is 50-80 mL.
In the preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode, the step (2) is Ni (OH)2The mass ratio of the potassium chloroplatinate to the potassium chloroplatinate is 1: 0.001-1, and the deionized water is 100-500 mL.
In the preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode, step (2) NaBH is adopted4The concentration of the solution is 0.01-10 g/mL, and the dosage is 10-1000 mL.
In the preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode, the tubular furnace in the step (3) is heated to 280-380 ℃ at a heating rate of 1-5 ℃/min.
According to the anode catalyst prepared by the preparation method, the Pt/NiO composite nano material is in an ultrathin layer structure, and the thickness is 2.0-2.5 nm; the Pt nanocrystal size is 2.6-3.0 nm.
A direct methanol fuel cell having an anode coated with the catalyst.
The invention has the beneficial effects that: the catalyst of the invention is firstly prepared by cyano gel-NaBH4Preparing nickel hydroxide ultrathin nanosheets by a reduction method; then loading superfine Pt nano-crystallites on the nickel hydroxide nano-sheets by a liquid phase in-situ reduction method; and finally, obtaining the superfine Pt nano microcrystal doped nickel oxide nanosheet material through high-temperature calcination.
The method has the advantages of simple and easy operation preparation process, low equipment requirement, uniform distribution of superfine Pt nano-crystallites, and capability of obviously improving the catalytic activity and the conductivity of the nickel oxide by only using a very small amount of Pt noble metal for doping, thereby showing excellent electrochemical reaction activity on the anode of the methanol fuel cell.
Using simple cyanogel-NaBH4The reduction method and the in-situ reduction method obtain the nickel oxide ultrathin nano flaky composite material loaded by the superfine Pt nano microcrystal with the superfine size.
Drawings
FIG. 1 is an AFM image of the Pt/NiO composite nanomaterial electrocatalyst prepared in example 1.
FIG. 2 is a TEM image of the Pt/NiO composite nanomaterial electrocatalyst prepared in example 1.
FIG. 3 is a LSV scan of the Pt/NiO composite nanomaterial electrocatalyst prepared in example 1 and pure NiO prepared in comparative example 1 in a 1MKOH +1M methanol electrolyte.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to the accompanying drawings.
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
The preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode comprises the following steps:
(1) preparation of Ni (OH)2Ultrathin nanosheet: firstly, dissolving 2mmol of nickel chloride and 1mmol of potassium nickel cyanide in 2mL of deionized water, uniformly stirring to obtain a mixed solution, and standing at room temperature for 6 hours to obtain blue mixed hydrogel; then 2g/mL reducer NaBH is added into the mixed hydrogel450mL of the solution is hydrothermally reduced at a constant temperature of 60 ℃ for 5h, cooled to room temperature, centrifuged and washed to obtain black Ni (OH)2Ultrathin nanosheets;
(2) preparation of Pt/Ni (OH)2The composite material comprises the following components: mixing the Ni (OH) obtained in the step (1)2Dispersing 10g and 2g of potassium chloroplatinate of the ultrathin nanosheet in 100mL of deionized water, then carrying out ultrasonic treatment for 10min, and adding 50mL of NaBH with the concentration of 0.1g/mL4Treating the solution in a constant-temperature water bath at 60 ℃ for 5h, centrifuging and collecting to obtain black Pt microcrystal loaded on Ni (OH)2Pt/Ni (OH) of ultrathin nanosheets2A composite material;
(3) preparing a Pt/NiO composite nano material: the Pt/Ni (OH) obtained in the step (2)2Placing the composite material in a tube furnace, annealing for 2 hours at 300 ℃ in the air, and naturally cooling to room temperature to obtain the composite materialAnd (3) Pt/NiO composite nano material.
It is dispersed in water and ethanol to obtain an electrocatalyst dispersion for use as an anode material in a direct methanol fuel cell.
As can be seen from FIG. 1, the NiO ultrathin flakes produced by the method described in this example 1 were only 1.8nm thick. The ultrathin lamellar structure can provide abundant surface catalytic active sites and is beneficial to improving the catalytic activity.
As can be seen from fig. 2, in example 1, the size of Pt nanocrystals is only about 3nm, and such small clusters greatly improve the utilization efficiency of noble metals, and at the same time, the defect of poor conductivity inherent in NiO can be improved by surface modification.
Example 2
The preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode comprises the following steps:
(1) preparation of Ni (OH)2Ultrathin nanosheet: firstly, dissolving 1mmol of nickel chloride and 0.5mmol of potassium nickel cyanide in 1mL of deionized water, uniformly stirring to obtain a mixed solution, and standing at room temperature for 8 hours to obtain blue mixed hydrogel; then 1g/mL reducer NaBH is added into the mixed hydrogel480mL of the solution is hydrothermally reduced at a constant temperature of 60 ℃ for 10h, cooled to room temperature, centrifuged and washed to obtain black Ni (OH)2Ultrathin nanosheets;
(2) preparation of Pt/Ni (OH)2The composite material comprises the following components: mixing the Ni (OH) obtained in the step (1)2Dispersing 5g and 0.5g of potassium chloroplatinate of the ultrathin nanosheet in 100mL of deionized water, then carrying out ultrasonic treatment for 10min, and adding 50mL of NaBH with the concentration of 0.05g/mL4Treating the solution in a constant-temperature water bath at 60 ℃ for 3h, centrifuging and collecting to obtain black Pt microcrystal loaded on Ni (OH)2Pt/Ni (OH) of ultrathin nanosheets2A composite material;
(3) preparing a Pt/NiO composite nano material: the Pt/Ni (OH) obtained in the step (2)2And placing the composite material in a tube furnace, annealing for 2 hours at 300 ℃ in the air, and naturally cooling to room temperature to obtain the Pt/NiO composite nano material.
It is dispersed in water and ethanol to obtain an electrocatalyst dispersion for use as an anode material in a direct methanol fuel cell.
Example 3
The preparation method of the transition metal-based catalyst for the direct methanol fuel cell anode comprises the following steps:
(1) preparation of Ni (OH)2Ultrathin nanosheet: firstly, dissolving 3mmol of nickel chloride and 1.5mmol of potassium nickel cyanide in 3mL of deionized water, uniformly stirring to obtain a mixed solution, and standing at room temperature for 10 hours to obtain blue mixed hydrogel; then 2g/mL reducer NaBH is added into the mixed hydrogel450mL of the solution is hydrothermally reduced at the constant temperature of 65 ℃ for 8h, cooled to room temperature, centrifuged and washed to obtain black Ni (OH)2Ultrathin nanosheets;
(2) preparation of Pt/Ni (OH)2The composite material comprises the following components: mixing the Ni (OH) obtained in the step (1)2Dispersing 10g and 1g of potassium chloroplatinate of the ultrathin nanosheet in 100mL of deionized water, then carrying out ultrasonic treatment for 10min, and adding 100mL of NaBH with the concentration of 0.05g/mL4Treating the solution in a constant-temperature water bath at 60 ℃ for 6h, centrifuging and collecting to obtain black Pt microcrystal loaded on Ni (OH)2Pt/Ni (OH) of ultrathin nanosheets2A composite material;
(3) preparing a Pt/NiO composite nano material: the Pt/Ni (OH) obtained in the step (2)2And placing the composite material in a tube furnace, annealing for 2 hours at 300 ℃ in the air, and naturally cooling to room temperature to obtain the Pt/NiO composite nano material.
It is dispersed in water and ethanol to obtain an electrocatalyst dispersion for use as an anode material in a direct methanol fuel cell.
Comparative example 1
The preparation method of the comparative catalyst comprises the following steps:
(1) preparation of Ni (OH)2Ultrathin nanosheet: firstly, dissolving 3mmol of nickel chloride and 1.5mmol of potassium nickel cyanide in 3mL of deionized water, uniformly stirring to obtain a mixed solution, and standing at room temperature for 10 hours to obtain blue mixed hydrogel; then 2g/mL reducer NaBH is added into the mixed hydrogel450mL of solution is hydrothermally reduced at the constant temperature of 65 ℃ for 8h, cooled to room temperature, centrifuged and washed to obtain blackNi(OH)2Ultrathin nanosheets;
(2) preparation of Ni (OH)2Materials: mixing the Ni (OH) obtained in the step (1)2Dispersing 10g of ultrathin nanosheet in 100mL of deionized water, then carrying out ultrasonic treatment for 10min, and adding 100mL of NaBH with the concentration of 0.05g/mL4Treating the solution in a constant temperature water bath at 60 ℃ for 6h, centrifuging and collecting to obtain Ni (OH)2Black powder;
(3) preparing a Pt/NiO composite nano material: the Pt/Ni (OH) obtained in the step (2)2And placing the composite material in a tube furnace, annealing for 2 hours at 300 ℃ in the air, and naturally cooling to room temperature to obtain the NiO nano material.
It is dispersed in water and ethanol to obtain an electrocatalyst dispersion for use as an anode material in a direct methanol fuel cell.
As can be seen from fig. 3, after the Pt nanocrystals are introduced, the difference of electronegativity causes electron cloud migration due to the synergistic effect between atoms, so that the electronic properties are changed, and the electrocatalytic oxidation of NiO on methanol is significantly increased.
Claims (9)
1. A method for preparing a transition metal-based catalyst for a direct methanol fuel cell anode, comprising the steps of:
(1) preparation of Ni (OH)2Ultrathin nanosheet: firstly, dissolving nickel chloride and potassium nickel cyanide in deionized water, uniformly stirring to obtain a mixed solution, and standing at room temperature to obtain blue mixed hydrogel; then adding a reducing agent NaBH into the mixed hydrogel4Carrying out hydrothermal reduction on the solution at a constant temperature of 60-65 ℃, cooling to room temperature, centrifuging and washing to obtain black Ni (OH)2Ultrathin nanosheets;
(2) preparation of Pt/Ni (OH)2The composite material comprises the following components: mixing the Ni (OH) obtained in the step (1)2Dispersing ultrathin nanosheets and potassium chloroplatinate in deionized water, and then adding NaBH4Treating the solution in a thermostatic water bath at 50-80 ℃ for 3-12 h, centrifuging and collecting to obtain black Pt microcrystal loaded on Ni (OH)2Pt/Ni (OH) of ultrathin nanosheets2A composite material;
(3) preparation of Pt/NiO compositeNano materials: the Pt/Ni (OH) obtained in the step (2)2And placing the composite material in a tubular furnace, annealing for 2-5 h at 280-380 ℃ in the air, and naturally cooling to room temperature to obtain the Pt/NiO composite nano material.
2. The method for preparing a transition metal-based catalyst for a direct methanol fuel cell anode according to claim 1, wherein the molar ratio of nickel chloride: potassium nickel cyanide is 2: 1; the deionized water is 1-100 mL.
3. The method for preparing the transition metal-based catalyst for the anode of the direct methanol fuel cell according to claim 1, wherein the step (1) is performed for 6-12 hours.
4. The method of claim 1, wherein the step (1) is a step of preparing a transition metal-based catalyst for an anode of a direct methanol fuel cell, wherein NaBH is added to the catalyst4The concentration of the solution is 0.1-2 g/mL, and the dosage is 50-80 mL.
5. The method of claim 1, wherein the step (2) comprises Ni (OH)2The mass ratio of the potassium chloroplatinate to the potassium chloroplatinate is 1: 0.001-1, and the deionized water is 100-500 mL.
6. The method of claim 1, wherein the step (2) is a step of preparing a transition metal-based catalyst for a direct methanol fuel cell anode using NaBH4The concentration of the solution is 0.01-10 g/mL, and the dosage is 10-1000 mL.
7. The method for preparing the transition metal-based catalyst for the anode of the direct methanol fuel cell according to claim 1, wherein the tube furnace in the step (3) is heated to 280-380 ℃ at a heating rate of 1-5 ℃/min.
8. The anode catalyst prepared by the preparation method of any one of claims 1 to 7, wherein the Pt/NiO composite nano material has an ultrathin sheet layer structure and the thickness of the Pt/NiO composite nano material is 2.0 to 2.5 nm; the Pt nanocrystal size is 2.6-3.0 nm.
9. A direct methanol fuel cell characterized in that the anode of the fuel cell is coated with the catalyst.
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| CN115532282A (en) * | 2022-10-10 | 2022-12-30 | 三峡大学 | Preparation method and application of hydroxide-loaded metal nanoparticles |
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| WO2008009742A1 (en) * | 2006-07-20 | 2008-01-24 | Acta S.P.A. | Anodic catalysts consisting of noble metals spontaneously deposited onto nanostructured catalysts composed of transition metals, their synthesis and use in fuel cells |
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