CN114583191A - Method for preparing anode catalyst of direct methanol fuel cell by electrodeposition - Google Patents

Method for preparing anode catalyst of direct methanol fuel cell by electrodeposition Download PDF

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CN114583191A
CN114583191A CN202210285191.5A CN202210285191A CN114583191A CN 114583191 A CN114583191 A CN 114583191A CN 202210285191 A CN202210285191 A CN 202210285191A CN 114583191 A CN114583191 A CN 114583191A
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electrodeposition
nitrogen
preparing
fuel cell
anode catalyst
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周健
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Shaanxi Ainuoweibang Information Technology Co ltd
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Shaanxi Ainuoweibang Information Technology Co ltd
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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 discloses a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition, which comprises the following steps: step 1: ultrasonically treating the carbon nano tube in mixed acid of concentrated sulfuric acid and concentrated nitric acid, soaking overnight, and drying at 80 ℃ for later use; carrying out nitrogen doping on the multi-walled carbon nano-tube by taking urea as a nitrogen source to prepare a nitrogen-doped carbon nano-tube material; using nitrogen-doped carbon nanotube as carrier, and electrodepositing metal ions in nitrogen-doped carbon nanotube by using chronoamperometryAiming loading of noble metal Pt and non-noble metal Co alloy particles on a carbon nanotube carrier is realized to prepare Pt3Co/N-CNTs anode catalyst. The method does not need to reduce the metal precursor by a chemical method, has short reaction time and simple operation, and the synthesized metal nano particles have high dispersity on the carrier and large specific surface area, and can effectively improve the catalytic activity of methanol electrooxidation and the CO poisoning resistance.

Description

Method for preparing anode catalyst of direct methanol fuel cell by electrodeposition
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition.
Background
A Direct Methanol Fuel Cell (DMFC) belongs to a low-temperature fuel cell, a proton exchange membrane is adopted as a solid electrolyte, and methanol is used as fuel. DMFC, as a potential clean energy source, can efficiently convert chemical energy into electrical energy to replace non-renewable fossil fuels, and can not only reduce the environmental crisis associated therewith, but also reduce the growing energy demand burden. Has attracted the attention of researchers as a promising renewable energy source; the DMFC single cell mainly comprises a membrane electrode, a bipolar plate, a collector plate and a sealing gasket. The membrane electrode composed of the catalyst layer and the proton exchange membrane is the core component of the fuel cell, and all the electrochemical reactions of the fuel cell are completed through the membrane electrode. The proton exchange membrane plays a role in conducting protons and blocking electrons, and simultaneously serves as a diaphragm to prevent permeation of bipolar fuels. The catalyst enables the reaction to proceed rapidly at low potentials by reducing the activation overpotential for the reaction. At present, the catalyst with better catalytic performance is a Pt-based supported catalyst, such as a Pt/C catalyst or a PtM/C alloy catalyst.
Currently, the main factors affecting the performance of DMFCs are: membrane thickness, cell temperature, methanol concentration, fuel pH, catalyst activity, electrode structure, low fuel utilization due to methanol permeation, formation of mixed potential at the cathode, and the like. The anode catalyst is low in activity and high in cost, which are the most critical factors influencing the application of the DMFC, and Pt is easy to adsorb oxygen-containing active intermediate CO generated in the methanol oxidation process to cause catalyst poisoning; therefore, in order to improve the catalytic performance of the anode and develop a new catalyst material, a method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition is provided.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the existing defects, and provide a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition, so as to solve the problems that the electrocatalyst provided in the background technology is low in activity and high in cost, and Pt is easy to adsorb oxygen-containing active intermediate CO generated by methanol oxidation to cause catalyst poisoning.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition comprises the following steps:
step 1: ultrasonically treating the carbon nano tube in a mixed acid of concentrated sulfuric acid and concentrated nitric acid, soaking overnight, and drying at 80 ℃ for later use;
step 2: ultrasonically dispersing a multi-walled carbon nanotube into 10mL of deionized water, adding urea into the deionized water, stirring and uniformly mixing, and performing rotary evaporation until the water is evaporated to dryness;
and 3, step 3: placing the precursor in a tube furnace, and calcining at high temperature in a nitrogen atmosphere to carry out nitrogen doping to obtain a nitrogen-doped carbon nanotube;
and 4, step 4: preparing a working electrode used in the electrodeposition process based on the obtained nitrogen-doped carbon nanotube carrier;
and 5: in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, and electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry.
Preferably, the carbon nanotubes selected in the step 1 are multiwall carbon nanotubes with a large specific surface area, and the ultrasonic time in the mixed acid is 0.5-2 h.
Preferably, the reaction temperature of the nitrogen doping reaction in the step 3 is 600-800 ℃, the heating rate is 2-5 ℃ per minute, and the reaction time is 0.5-2 hours.
Preferably, in the step 5, before electrodeposition by adopting a chronoamperometry, nitrogen is introduced into the electrolyte for 20-50 min, and the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2O (0.5 to 50mmol/L) in the mixture.
Preferably, in the step 5, when the catalyst is prepared by electrodeposition by a chronoamperometry, the deposition potential is-0.3-0.5V, and the current electrifying time is 300-1200 s.
Preferably, the mass ratio of urea to carbon nanotubes in the step 2 is 1: 1.
Preferably, the working electrode prepared in the step 4 is dried for 3-8 hours at the temperature of 110 ℃.
Preferably, the step 4 comprises the following steps:
step 4.1: grinding and uniformly mixing the nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 2;
step 4.2: then 0.15-0.25 mL of azomethyl pyrrolidone is dripped to grind the azomethyl pyrrolidone into carbon slurry;
step 4.3: and uniformly coating the carbon slurry on 2 x 2cm carbon paper, a titanium plate which is polished in advance or the surface of other conductive machine bodies.
Preferably, the molar ratio of Pt to Co in the electrolyte is 5:1 to 1: 5.
Preferably, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step 1 is 1-5: 1.
Compared with the prior art, the invention provides a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition, which has the following beneficial effects:
1. according to the invention, the metal ions are electrodeposited on the nitrogen-doped carbon nanotube carrier by adopting a chronoamperometry, the metal precursor is not required to be reduced by a chemical method, the reaction time is short, and the operation is simple;
2. the method takes urea as a nitrogen source to carry out nitrogen doping on the multi-walled carbon nano-tube to prepare a nitrogen-doped carbon nano-tube material; pt prepared by loading noble metal Pt and non-noble metal Co alloy particles on nitrogen-doped carbon nanotube3The Co/N-CNTs anode catalyst has high dispersion degree of synthesized metal nano particles on a carrier, has large specific surface area, and can effectively improve the catalytic activity for methanol electrooxidation and the CO poisoning resistance.
Drawings
FIG. 1 shows Pt prepared in examples 1, 2, 3 and 43XRD patterns of Co/N-CNTs and commercial Pt/C;
FIG. 2 shows Pt prepared in examples 1, 2, 3 and 43HRTEM images of Co/N-CNTs and commercial Pt/C;
FIG. 3 shows Pt prepared in examples 1, 2, 3 and 43Co/N-CNTs and commercial Pt/C at 0.5M H2SO4And 1M CH3Cyclic voltammetry profile in OH solution;
FIG. 4 shows Pt prepared in examples 1, 2, 3 and 43CO elution profiles for Co/N-CNTs and commercial Pt/C.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention provides a technical scheme that: a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition comprises the following steps:
step 1: ultrasonically treating the carbon nano tube in mixed acid of concentrated sulfuric acid and concentrated nitric acid, soaking overnight, and drying at 80 ℃ for later use;
step 2: ultrasonically dispersing a multi-walled carbon nanotube into 10mL of deionized water, adding urea into the deionized water, stirring and uniformly mixing a mixture of the carbon nanotube and the urea, and performing rotary evaporation until the water is evaporated to dryness;
and step 3: placing the precursor in a tube furnace, and calcining at high temperature in a nitrogen atmosphere to carry out nitrogen doping to obtain a nitrogen-doped carbon nanotube;
and 4, step 4: preparing a working electrode used in the electrodeposition process based on the obtained nitrogen-doped carbon nanotube carrier;
and 5: in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, and electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry.
In the invention, preferably, the carbon nanotubes selected in the step 1 are multi-wall carbon nanotubes with a large specific surface area, and the ultrasonic time in the mixed acid is 0.5-2 h.
In the invention, preferably, the reaction temperature of the nitrogen doping reaction in the step 3 is 600-800 ℃, the heating rate is 2-5 ℃ per minute, and the reaction time is 0.5-2 hours.
In the invention, preferably, in the step 5, before electrodeposition by adopting a chronoamperometry method, nitrogen is introduced into the electrolyte for 20-50 min, and the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2O (0.5 to 50mmol/L) in the mixture.
In the invention, preferably, when the catalyst is prepared by electrodeposition in the step 5 by a chronoamperometry, the deposition potential is-0.3V, and the current electrifying time is 1200 s.
In the present invention, it is preferable that the mass ratio of urea to carbon nanotubes in step 2 is 1: 1.
In the invention, preferably, the working electrode prepared in the step 4 is dried for 3-8 hours at the temperature of 110 ℃.
In the present invention, preferably, step 4 includes the steps of:
step 4.1: grinding and uniformly mixing the nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 2;
step 4.2: then 0.15-0.25 mL of azomethyl pyrrolidone is dripped to grind the azomethyl pyrrolidone into carbon slurry;
step 4.3: and uniformly coating the carbon slurry on 2 x 2cm carbon paper, a titanium plate which is polished in advance or the surface of other conductive machine bodies.
In the present invention, the molar ratio of Pt to Co in the electrolyte is preferably 5:1 to 1: 5.
In the present invention, it is preferable that the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step 1 is 1: 1.
The working principle and the using process of the invention are as follows: when the carbon nano tube precursor is used, a multi-walled carbon nano tube with a large specific surface area is selected to be subjected to ultrasonic treatment in mixed acid of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 1:1, the ultrasonic treatment time in the mixed acid is 0.5-2 h, the multi-walled carbon nano tube precursor is soaked overnight and dried at 80 ℃ for later use, then the multi-walled carbon nano tube precursor is subjected to ultrasonic dispersion in 10mL of deionized water, urea is added into the mixed acid, the mixture of the carbon nano tube and the urea is stirred and mixed uniformly, the mixture is rotated to evaporate water until the water is evaporated to dryness, wherein the mass ratio of the urea to the carbon nano tube is 1:1, the precursor is placed in a tube furnace, and the precursor is driedCalcining at 600-800 ℃ under nitrogen atmosphere for nitrogen doping, wherein the heating rate is 2-5 ℃ per minute, the reaction time is 0.5-2 hours, so as to obtain nitrogen-doped carbon nanotubes, uniformly grinding and mixing the obtained nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:2, dropwise adding 0.15-0.25 mL of azomethyl pyrrolidone, grinding the mixture into carbon slurry, uniformly coating the carbon slurry on 2 x 2cm carbon paper, a titanium plate which is polished in advance or the surface of other conductive machine bodies, preparing a working electrode used in the electrodeposition process, drying the working electrode at 110 ℃ for 3-8 hours, introducing 20-50 min of nitrogen into the electrolyte, and preparing the electrolyte H in advance2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2And O (0.5-50 mmol/L) mixture, wherein the molar ratio of Pt to the Pt in the electrolyte is 5: 1-1: 5, in the prepared electrolyte, performing electrodeposition by using the working electrode as a cathode, a platinum sheet electrode as an anode and a saturated calomel electrode as a reference electrode at the temperature of 20-60 ℃ through a Co current method, wherein the deposition potential is-0.3V, and the current energization time is 1200s to prepare the catalyst.
Example 2
The invention provides a technical scheme that: a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition comprises the following steps:
step 1: ultrasonically treating the carbon nano tube in mixed acid of concentrated sulfuric acid and concentrated nitric acid, soaking overnight, and drying at 80 ℃ for later use;
step 2: ultrasonically dispersing a multi-walled carbon nanotube into 10mL of deionized water, adding urea into the deionized water, stirring and uniformly mixing a mixture of the carbon nanotube and the urea, and performing rotary evaporation until the water is evaporated to dryness;
and step 3: placing the precursor in a tube furnace, and calcining at high temperature in a nitrogen atmosphere to carry out nitrogen doping to obtain a nitrogen-doped carbon nanotube;
and 4, step 4: preparing a working electrode used in the electrodeposition process based on the obtained nitrogen-doped carbon nanotube carrier;
and 5: in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, and electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry.
In the invention, preferably, the carbon nanotubes selected in the step 1 are multi-wall carbon nanotubes with a large specific surface area, and the ultrasonic time in the mixed acid is 0.5-2 h.
In the invention, preferably, the reaction temperature of the nitrogen doping reaction in the step 3 is 600-800 ℃, the heating rate is 2-5 ℃ per minute, and the reaction time is 0.5-2 hours.
In the invention, preferably, in the step 5, before electrodeposition by adopting a chronoamperometry method, nitrogen is introduced into the electrolyte for 20-50 min, and the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2O (0.5 to 50mmol/L) in the mixture.
In the present invention, preferably, in the step 5, the deposition potential is 0.2V and the current-carrying time is 750s when the catalyst is prepared by electrodeposition by a chronoamperometry.
In the present invention, it is preferable that the mass ratio of urea to carbon nanotubes in step 2 is 1: 1.
In the invention, preferably, the working electrode prepared in the step 4 is dried for 3-8 hours at the temperature of 110 ℃.
In the present invention, preferably, step 4 includes the steps of:
step 4.1: grinding and uniformly mixing the nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 2;
step 4.2: then 0.15-0.25 mL of azomethyl pyrrolidone is dripped to grind the azomethyl pyrrolidone into carbon slurry;
step 4.3: and uniformly coating the carbon slurry on 2 x 2cm carbon paper, a titanium plate which is polished in advance or the surface of other conductive machine bodies.
In the present invention, the molar ratio of Pt to Co in the electrolyte is preferably 5:1 to 1: 5.
In the present invention, it is preferable that the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step 1 is 3: 1.
The working principle and the using process of the invention are as follows: when in use, the medicine is selectedCarrying out ultrasonic treatment on multi-walled carbon nanotubes with large specific surface area in mixed acid of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 for 0.5-2 h, soaking overnight, drying at 80 ℃ for later use, then carrying out ultrasonic dispersion on the multi-walled carbon nanotubes in 10mL of deionized water, adding urea, stirring and uniformly mixing the carbon nanotubes and the urea mixture, carrying out rotary evaporation until the water is evaporated to dryness, wherein the mass ratio of the urea to the carbon nanotubes is 10:1, placing the precursor in a tubular furnace, carrying out nitrogen doping at 600-800 ℃ under nitrogen atmosphere by high-temperature calcination at a heating rate of 2-5 ℃ per minute for 0.5-2 h to obtain nitrogen-doped carbon nanotubes, grinding and uniformly mixing the obtained nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) in a mass ratio of 8:2, dropwise adding 0.15-0.25 mL of N-methyl pyrrolidone, grinding the nitrogen-doped carbon nanotubes into carbon slurry, uniformly coating carbon slurry on 2 x 2cm carbon paper, a titanium plate polished in advance or the surface of other conductive organisms, preparing a working electrode used in the electrodeposition process, drying the working electrode at 110 ℃ for 3-8H, introducing nitrogen into the electrolyte for 20-50 min, wherein the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2And O (0.5-50 mmol/L) mixture, wherein the molar ratio of Pt to Co in the electrolyte is 5: 1-1: 5, in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry, the deposition potential is 0.2V, and the current energization time is 750s, so as to prepare the catalyst.
Example 3
The invention provides a technical scheme that: a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition comprises the following steps:
step 1: ultrasonically treating the carbon nano tube in mixed acid of concentrated sulfuric acid and concentrated nitric acid, soaking overnight, and drying at 80 ℃ for later use;
step 2: ultrasonically dispersing a multi-walled carbon nanotube into 10mL of deionized water, adding urea into the deionized water, stirring and uniformly mixing a mixture of the carbon nanotube and the urea, and performing rotary evaporation until the water is evaporated to dryness;
and 3, step 3: placing the precursor in a tube furnace, and calcining at high temperature in a nitrogen atmosphere to carry out nitrogen doping to obtain a nitrogen-doped carbon nanotube;
and 4, step 4: preparing a working electrode used in the electrodeposition process based on the obtained nitrogen-doped carbon nanotube carrier;
and 5: in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, and electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry.
In the invention, preferably, the carbon nanotubes selected in the step 1 are multi-walled carbon nanotubes with large specific surface area, and the ultrasonic time in the mixed acid is 0.5-2 h.
In the invention, preferably, the reaction temperature of the nitrogen doping reaction in the step 3 is 600-800 ℃, the heating rate is 2-5 ℃ per minute, and the reaction time is 0.5-2 hours.
In the invention, preferably, in the step 5, before electrodeposition by adopting a chronoamperometry method, nitrogen is introduced into the electrolyte for 20-50 min, and the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2O (0.5 to 50mmol/L) in the mixture.
In the present invention, preferably, in the step 5, when the catalyst is prepared by electrodeposition by a chronoamperometry, the deposition potential is 0.5V, and the current energization time is 300 s.
In the present invention, it is preferable that the mass ratio of urea to carbon nanotubes in step 2 is 1: 1.
In the invention, preferably, the working electrode prepared in the step 4 is dried for 3-8 hours at the temperature of 110 ℃.
In the present invention, preferably, step 4 includes the steps of:
step 4.1: grinding and uniformly mixing the nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 2;
step 4.2: then, 3-5 drops of N-methyl pyrrolidone are dripped to grind the mixture into carbon slurry;
step 4.3: and uniformly coating the carbon slurry on 2 x 2cm carbon paper, a titanium plate which is polished in advance or the surface of other conductive machine bodies.
In the present invention, the molar ratio of Pt to Co in the electrolyte is preferably 5:1 to 1: 5.
In the present invention, it is preferable that the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step 1 is 5: 1.
The working principle and the using process of the invention are as follows: when in use, the multiwall carbon nanotube with larger specific surface area is selected to be subjected to ultrasonic treatment in mixed acid of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 5:1, the ultrasonic treatment time in the mixed acid is 0.5-2 h, the multiwall carbon nanotube is soaked overnight and dried at 80 ℃ for standby use, then the multiwall carbon nanotube is subjected to ultrasonic dispersion in 10mL of deionized water, urea is added into the mixture, the stirring speed of the mixture of the carbon nanotube and the urea is 2-5 ℃ per minute, the reaction time is 0.5-2 h, nitrogen-doped carbon nanotubes are obtained, the nitrogen-doped carbon nanotubes are uniformly stirred and mixed, the mixture is rotated and evaporated until the moisture is evaporated to dryness, wherein the mass ratio of the urea to the carbon nanotube is 20:1, the precursor is placed in a tubular furnace, nitrogen doping is performed by high-temperature calcination at 600-800 ℃ under the nitrogen atmosphere, the heated nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) are uniformly ground and mixed in a mass ratio of 8:2, 3-5 drops of azomethylpyrrolidone are dripped to grind the carbon slurry, uniformly coating carbon slurry on 2 x 2cm carbon paper, a titanium plate polished in advance or the surface of other conductive organisms, preparing a working electrode used in the electrodeposition process, drying the working electrode at 110 ℃ for 3-8H, introducing nitrogen into the electrolyte for 20-50 min, wherein the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2And O (0.5-50 mmol/L) mixture, wherein the molar ratio of Pt to Co in the electrolyte is 5: 1-1: 5, in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry, the deposition potential is 0.5V, and the current electrifying time is 300s, so as to prepare the catalyst.
Example 4
The invention provides a technical scheme that: a method for preparing a direct methanol fuel cell anode catalyst by electrodeposition comprises the following steps:
step 1: ultrasonically treating the carbon nano tube in mixed acid of concentrated sulfuric acid and concentrated nitric acid, soaking overnight, and drying at 80 ℃ for later use;
step 2: ultrasonically dispersing a multi-walled carbon nanotube into 10mL of deionized water, adding urea into the deionized water, stirring and uniformly mixing a mixture of the carbon nanotube and the urea, and performing rotary evaporation until the water is evaporated to dryness;
and step 3: placing the precursor in a tube furnace, and calcining at high temperature in a nitrogen atmosphere to carry out nitrogen doping to obtain a nitrogen-doped carbon nanotube;
and 4, step 4: preparing a working electrode used in the electrodeposition process based on the obtained nitrogen-doped carbon nanotube carrier;
and 5: in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, and electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry.
In the invention, preferably, the carbon nanotubes selected in the step 1 are multi-wall carbon nanotubes with a large specific surface area, and the ultrasonic time in the mixed acid is 0.5-2 h.
In the invention, preferably, the reaction temperature of the nitrogen doping reaction in the step 3 is 600-800 ℃, the heating rate is 2-5 ℃ per minute, and the reaction time is 0.5-2 hours.
In the invention, preferably, in the step 5, before electrodeposition by adopting a chronoamperometry method, nitrogen is introduced into the electrolyte for 20-50 min, and the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2O (0.5 to 50mmol/L) in the mixture.
In the present invention, preferably, in the step 5, the deposition potential is 0.2V and the current electrifying time is 1000s when the catalyst is prepared by electrodeposition by a chronoamperometry.
In the present invention, it is preferable that the mass ratio of urea to carbon nanotubes in step 2 is 1: 1.
In the invention, preferably, the working electrode prepared in the step 4 is dried for 3-8 hours at the temperature of 110 ℃.
In the present invention, preferably, step 4 includes the steps of:
step 4.1: grinding and uniformly mixing the nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 2;
and 4.2: then 0.15-0.25 mL of azomethyl pyrrolidone is dripped to grind the azomethyl pyrrolidone into carbon slurry;
step 4.3: and uniformly coating the carbon slurry on 2 x 2cm carbon paper, a titanium plate which is polished in advance or the surface of other conductive machine bodies.
In the present invention, the molar ratio of Pt to Co in the electrolyte is preferably 5:1 to 1: 5.
In the present invention, it is preferable that the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step 1 is 1 to 5: 1.
The working principle and the using process of the invention are as follows: when the preparation method is used, the multiwalled carbon nanotubes with large specific surface area are selected to be subjected to ultrasonic treatment in mixed acid of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1-5: 1, the ultrasonic treatment time in the mixed acid is 0.5-2 h, the multiwalled carbon nanotubes are soaked overnight and dried at 80 ℃ for later use, then the multiwalled carbon nanotubes are subjected to ultrasonic dispersion in 10mL of deionized water, urea is added into the mixture, the mixture of the carbon nanotubes and the urea is stirred and mixed uniformly, the mixture is rotated and evaporated until the moisture is evaporated to dryness, wherein the mass ratio of the urea to the carbon nanotubes is 1:1, the precursor is placed into a tubular furnace, nitrogen doping is carried out by high-temperature calcination at 600-800 ℃ under the nitrogen atmosphere, the heating rate is 2-5 ℃ per minute, the reaction time is 0.5-2 h, the nitrogen-doped carbon nanotubes are obtained, the obtained nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) are ground and mixed uniformly according to the mass ratio of 8:2, 3-5 drops of azomethylpyrrolidone are dripped to grind the carbon slurry, uniformly coating carbon slurry on 2 x 2cm carbon paper, a titanium plate polished in advance or the surface of other conductive organisms, preparing a working electrode used in the electrodeposition process, drying the working electrode at 110 ℃ for 3-8H, introducing nitrogen into the electrolyte for 20-50 min, wherein the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2O (0.5-50 mmol/L) mixture, and the mole of Pt and Co in the electrolyteThe molar ratio is 5: 1-1: 5, and the catalyst is prepared by taking the working electrode as a cathode, a platinum sheet electrode as an anode and a saturated calomel electrode as a reference electrode in a prepared electrolyte and carrying out electrodeposition by a chronoamperometry at the temperature of 20-60 ℃ with the deposition potential of 0.2V and the current energization time of 1000 s.
The direct methanol fuel cell anode catalysts prepared in the above examples 1, 2, 3 and 4 were characterized by XRD, TEM and HRTEM for structural characteristics and chemical properties of the catalysts, and by three-electrode system for electrocatalyst activity.
Pt prepared as shown in FIG. 1 for examples 1, 2, 3 and 43XRD of Co/N-CNT, it can be seen from the figure that all samples have the same crystal structure, and diffraction peaks appear at 40.3 and 47.1 positions, and are similar to Pt3The (111) and (200) crystal planes of the Co alloy correspond to each other, and Pt is proved3The face centered cubic (fcc) structure of Co NPs indicates that Pt is successfully loaded on the surface of the carrier by an electrodeposition method3Co NPs。
FIG. 2 shows Pt prepared in examples 1, 2, 3 and 43TEM image of Co/N-CNT, it is known that metal nanoparticles can be uniformly deposited on the surface of the catalyst support by electrodeposition, and the lattice spacing of the metal nanoparticles is 0.22nm, corresponding to Pt3Co (111) plane, further illustrating the successful synthesis of catalyst Pt by electrodeposition3Co/N-CNT with metal nanoparticles in ordered Pt3Co nanoparticles are present.
The performances of the electrocatalytic Methanol Oxidation (MOR) catalysts under the same conditions were compared with those of a commercial Pt/C catalyst at 0.5M H2SO4And 1MCH3In OH solution, the cyclic voltammogram is tested at-0.2V-1.0V at a sweep rate of 50mv/s, as shown in FIG. 3, it can be seen from FIG. 3 that an oxidation peak appears at about 0.6V, and compared with commercial Pt/C, the direct methanol fuel cell anode catalysts prepared in examples 1, 2, 3 and 4 show better electrocatalytic methanol oxidation performance, and the current density can reach 3.2 times of that of commercial Pt/C. The current densities are summarized in the following table:
Figure RE-GDA0003618858710000131
it can be known from comparison that the anode catalysts of the direct methanol fuel cells prepared in examples 1, 2, 3 and 4 can significantly improve the efficiency of methanol electrooxidation. The doped N atoms can target metal nano particles, and metal ions are electrodeposited on the nitrogen-doped carbon nano tube carrier by adopting a timing current method, the metal precursor is not required to be reduced by a chemical method, the reaction time is short, and the operation is simple;
it can be seen from the comparison of the test CO dissolution curves that the direct methanol fuel cell anode catalysts prepared by examples 1, 2, 3 and 4 have lower oxidation peak potentials than commercial Pt/C, which indicates that CO generated during the electrocatalysis process is easier to remove and the catalysts show better resistance to CO poisoning.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. A method for preparing a direct methanol fuel cell anode catalyst by electrodeposition is characterized by comprising the following steps: the preparation process comprises the following steps:
step 1: ultrasonically treating the carbon nano tube in mixed acid of concentrated sulfuric acid and concentrated nitric acid, soaking overnight, and drying at 80 ℃ for later use;
step 2: ultrasonically dispersing a multi-walled carbon nanotube into 10mL of deionized water, adding urea into the deionized water, stirring and uniformly mixing a mixture of the carbon nanotube and the urea, and performing rotary evaporation until the water is evaporated to dryness;
and step 3: placing the precursor in a tube furnace, and calcining at high temperature in a nitrogen atmosphere to carry out nitrogen doping to obtain a nitrogen-doped carbon nanotube;
and 4, step 4: preparing a working electrode used in the electrodeposition process based on the obtained nitrogen-doped carbon nanotube carrier;
and 5: in the prepared electrolyte, the working electrode is used as a cathode, a platinum sheet electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, and electrodeposition is carried out at the temperature of 20-60 ℃ by a chronoamperometry.
2. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: the carbon nano tube selected in the step 1 is a multi-wall carbon nano tube with a large specific surface area, and the ultrasonic time in the mixed acid is 0.5-2 h.
3. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: in the step 3, the reaction temperature of the nitrogen doping reaction is 600-800 ℃, the heating rate is 2-5 ℃ per minute, and the reaction time is 0.5-2 hours.
4. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: in the step 5, before electrodeposition by adopting a chronoamperometry method, nitrogen is introduced into the electrolyte for 20-50 min, and the prepared electrolyte is H2PtCl6·6H2O (0.5-50 mmol/L) and Co (NO)3)2·6H2O (0.5 to 50mmol/L) in the mixture.
5. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: and in the step 5, when the catalyst is prepared by electrodeposition by a chronoamperometry method, the deposition potential is-0.3-0.5V, and the current electrifying time is 300-1200 s.
6. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: the mass ratio of the urea to the carbon nano tubes in the step 2 is 1: 1.
7. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: and in the step 4, the prepared working electrode is dried for 3-8 hours at the temperature of 110 ℃.
8. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: the step 4 comprises the following steps:
step 4.1: grinding and uniformly mixing the nitrogen-doped carbon nanotube carrier and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 2;
step 4.2: then 0.15-0.25 mL of azomethyl pyrrolidone is dripped to grind the azomethyl pyrrolidone into carbon slurry;
step 4.3: and uniformly coating the carbon slurry on 2 x 2cm carbon paper, a titanium plate which is polished in advance or the surface of other conductive machine bodies.
9. The method for preparing the anode catalyst of the direct methanol fuel cell by the electrodeposition as claimed in claim 4, wherein: the molar ratio of Pt to Co in the electrolyte is 5:1 to 1: 5.
10. The method for preparing the anode catalyst of the direct methanol fuel cell by electrodeposition according to claim 1, wherein: the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step 1 is 1-5: 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020718A (en) * 2022-06-14 2022-09-06 太原理工大学 Non-noble metal nano catalyst for methanol oxidation reaction and preparation method thereof
CN115069289A (en) * 2022-07-07 2022-09-20 青岛科技大学 Preparation method of hydrazine hydrate dehydrogenation catalyst
CN115353094A (en) * 2022-07-18 2022-11-18 北京市科学技术研究院资源环境研究所 Solid phase purification method of carbon nano tube

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020718A (en) * 2022-06-14 2022-09-06 太原理工大学 Non-noble metal nano catalyst for methanol oxidation reaction and preparation method thereof
CN115020718B (en) * 2022-06-14 2024-02-13 太原理工大学 Non-noble metal nano-catalyst for methanol oxidation reaction and preparation method thereof
CN115069289A (en) * 2022-07-07 2022-09-20 青岛科技大学 Preparation method of hydrazine hydrate dehydrogenation catalyst
CN115353094A (en) * 2022-07-18 2022-11-18 北京市科学技术研究院资源环境研究所 Solid phase purification method of carbon nano tube

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