CN104953134A - Preparation method of electrocatalyst of direct methanol fuel cell (DMFC) - Google Patents
Preparation method of electrocatalyst of direct methanol fuel cell (DMFC) Download PDFInfo
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- CN104953134A CN104953134A CN201510362707.1A CN201510362707A CN104953134A CN 104953134 A CN104953134 A CN 104953134A CN 201510362707 A CN201510362707 A CN 201510362707A CN 104953134 A CN104953134 A CN 104953134A
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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
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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
- H01M4/96—Carbon-based electrodes
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- 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 relates to a preparation method of an electrocatalyst of a direct methanol fuel cell (DMFC). The preparation method comprises the following steps: dispersing graphene oxide and a monomer in an HAc-NaAc buffer solution to obtain mixed liquor of the monomer and graphene oxide; carrying out cyclic voltammetry scan on the mixed liquor of the monomer and graphene oxide to obtain a conducting polymer loaded and reduced graphene oxide composite material modified electrode; by using the electrode as a working electrode and a thiol solution as an electrolyte, carrying out cyclic voltammetry scan by adopting a three-electrode system to obtain a thiolated conducting polymer loaded and reduced graphene oxide composite material modified electrode; by using the electrode as a working electrode and a metal salt solution as an electrolyte, carrying out constant potential reduction by adopting the three-electrode system to obtain the electrocatalyst of the DMFC on the working electrode. The preparation method adopts an electrochemical method and is simple in operating steps. The obtained catalyst has high metal particle dispersibility and small particle size and has high electroactivity and stability.
Description
Technical field
The present invention relates to fuel cell electro-catalyst technical field, particularly relate to a kind of preparation method of Electro Catalysts for Direct Methanol Fuel Cells.
Background technology
Direct methanol fuel cell is a kind of novel environment friendly device that chemical energy can be converted to electric energy, have that price is comparatively cheap, raw material sources extensively, store and the advantage such as transport is safer.But the noble metal catalyst that direct methanol fuel cell uses is very rare, expensive; Carbon carrier such as carbon black, carbon fiber, carbon nano-tube, Graphene even load type catalyst is adopted can greatly to reduce noble-metal-supported amount, improve its utilance simultaneously, but the defect of this kind of carrier itself makes noble metal nano particles large, and noble metal nano particles is made to occur agglomeration and have a strong impact on catalytic efficiency largely.
Summary of the invention
Based on this, be necessary to provide a kind of noble metal nano particles dispersiveness obtained high and the preparation method of the Electro Catalysts for Direct Methanol Fuel Cells that particle diameter is little.
A preparation method for Electro Catalysts for Direct Methanol Fuel Cells, comprises step:
By graphene oxide and monomer dispersion in HAc-NaAc cushioning liquid, obtain the mixed liquor of monomer and graphene oxide;
With the first electrode for work electrode, the mixed liquor of three-electrode system to described monomer and graphene oxide is adopted to carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load conducting polymer is modified;
The electrode modified with the redox graphene composite material of described load conducting polymer is for work electrode, thiol solution is electrolyte, three-electrode system is adopted to carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load sulfhydrylation conducting polymer is modified; And
The electrode modified with the redox graphene composite material of described load sulfhydrylation conducting polymer is for work electrode, metal salt solution is electrolyte, adopt three-electrode system to carry out constant potential reduction, obtain described Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
The preparation method of above-mentioned Electro Catalysts for Direct Methanol Fuel Cells, electrochemical method is adopted to make monomer oxidation and reduced by graphene oxide, make conducting polymer sulfhydrylation, and on the conducting polymer-redox graphene composite material of sulfhydrylation original position electroreduction slaine, operating procedure is simple, efficiency is high, environmental protection, the Electro Catalysts for Direct Methanol Fuel Cells obtained is the conducting polymer composite material of the sulfhydrylation of carrying metal particles, improve dispersiveness and the stability of metallic, its metallic particles dispersiveness is high, particle diameter is little is 80-100nm, can be used for direct methanol fuel cell, and there is high electroactive and high stability, the oxidation current of catalysis methanol reaches 22mA mg
pt -1.
Wherein in an embodiment, the pH value of described HAc-NaAc cushioning liquid is 4-6.
Wherein in an embodiment, described first electrode is any one in glass-carbon electrode, graphite electrode, carbon fiber electrode, carbon cloth electrode and carbon paste electrode, and described monomer is any one in aniline, pyrroles and thiophene.
Wherein in an embodiment, described with the first electrode for work electrode, adopt the mixed liquor of three-electrode system to described monomer and graphene oxide to carry out cyclic voltammetry scan, the concrete steps of the electrode that the redox graphene composite material obtaining load conducting polymer is modified are:
The mixed liquor of described monomer and graphene oxide is added drop-wise on described first electrode, dry, again with described first electrode be work electrode, to electrode be platinum plate electrode, reference electrode is for saturated calomel electrode, be placed in electrolyte solution and carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining described load conducting polymer is modified.
Wherein in an embodiment, described with the first electrode for work electrode, adopt the mixed liquor of three-electrode system to described monomer and graphene oxide to carry out cyclic voltammetry scan, the concrete steps of the electrode that the redox graphene composite material obtaining load conducting polymer is modified are:
With the first electrode be work electrode, to electrode be platinum plate electrode, reference electrode is for saturated calomel electrode, the mixed liquor being placed in described monomer and graphene oxide carries out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining described load conducting polymer is modified.
Wherein in an embodiment, described with the first electrode for work electrode, the scanning current potential adopting the mixed liquor of three-electrode system to described monomer and graphene oxide to carry out cyclic voltammetry scan is-1.0V to 0.85V, and sweep speed is 20-100mV/s.
Wherein in an embodiment, the described electrode modified with the redox graphene composite material of load conducting polymer is for work electrode, thiol solution is electrolyte, three-electrode system is adopted to carry out cyclic voltammetry scan, in the step of the electrode that the redox graphene composite material obtaining load sulfhydrylation conducting polymer is modified:
Be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and described thiol solution is the mixed solution of mercaptan in mixed solvent, and wherein mercaptan is DMcT, the concentration of DMcT is 0.01-0.5mg/mL, and mixed solvent is volume ratio is the absolute ethyl alcohol of 1:1 and the mixed liquor of 0.2mol/L sulfuric acid.
Wherein in an embodiment, the described electrode modified with the redox graphene composite material of load conducting polymer is for work electrode, thiol solution is electrolyte, and the scanning current potential adopting three-electrode system to carry out cyclic voltammetry scan is-0.2V to 0.8V, and sweep speed is 20-100mV/s.
Wherein in an embodiment, the described electrode modified with the redox graphene composite material of load sulfhydrylation conducting polymer is for work electrode, metal salt solution is electrolyte, adopt three-electrode system to carry out constant potential reduction, obtain in the step of described Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s:
Be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and described metal salt solution is the mixed solution of sulfuric acid, ethylene glycol and chloroplatinate or the mixed solution for sulfuric acid, ethylene glycol, chloroplatinate and ruthenium trichloride.
Wherein in an embodiment, the described electrode modified with the redox graphene composite material of load sulfhydrylation conducting polymer is for work electrode, metal salt solution is electrolyte, and the current potential adopting three-electrode system to carry out constant potential reduction is-0.7 to-0.3V, and electrolysis time is 30-200s.
Accompanying drawing explanation
Fig. 1 is the step schematic diagram of the preparation method of the Electro Catalysts for Direct Methanol Fuel Cells of an execution mode;
Fig. 2 is the scanning electron microscope (SEM) photograph of the Electro Catalysts for Direct Methanol Fuel Cells that embodiment 1 obtains;
Fig. 3 is the cyclic voltammogram of the Electro Catalysts for Direct Methanol Fuel Cells that embodiment 1 obtains.
Embodiment
For the ease of understanding the present invention, below with reference to relevant drawings, the present invention is described more fully.Preferred embodiment of the present invention is given in accompanying drawing.But the present invention can realize in many different forms, is not limited to embodiment described herein.On the contrary, provide the object of these embodiments be make the understanding of disclosure of the present invention more comprehensively thorough.
With reference to Fig. 1, the preparation method of the Electro Catalysts for Direct Methanol Fuel Cells of an execution mode, comprising:
Step S100: by graphene oxide and monomer dispersion in HAc-NaAc (Acetic acid-sodium acetate) cushioning liquid, obtain the mixed liquor of monomer and graphene oxide.
By graphene oxide and monomer dispersion in HAc-NaAc cushioning liquid, obtain the mixed liquor of monomer and graphene oxide
Graphene is a kind of Two-dimensional Carbon material, it is the general designation of single-layer graphene, bilayer graphene and few layer graphene, due to the electronics of its excellence, machinery and thermal stability, the application in battery, electronic device, transducer and composite material obtains the extensive concern of people.Graphene oxide (graphene oxide) is the oxide of Graphene, and on graphene oxide, oxygen-containing functional group increases and makes its character more active than Graphene.Redox graphene: by by the carboxyl on graphene oxide and carbonyl reduction, too can not be reduced into Graphene again, it is more more active than Graphene that it had both had part oxygen-containing functional group, again than graphene oxide good stability.
Wherein in an embodiment, monomer is any one in aniline, pyrroles and thiophene.Because the easy oxidation color of monomer deepens, need to carry out purification process before therefore using.As the concrete steps of aniline being carried out to purifying are: distill under the condition of heating and nitrogen protection aniline, then continue distillation to the cut that obtains, until cut is colourless, keep in Dark Place in 4 DEG C for subsequent use.
Wherein in an embodiment, step S100 is specially: be dispersed in by graphene oxide in HAc-NaAc cushioning liquid, and the concentration of graphene oxide in HAc-NaAc cushioning liquid is 1mg/mL.Add monomer again, obtain the mixed liquor of monomer and graphene oxide, wherein the concentration of monomer is 0.01-0.1mol/L.
Wherein in an embodiment, the pH value of HAc-NaAc cushioning liquid is 4-6.
Wherein in an embodiment, graphene oxide adopts Hummers legal system standby, and Hummers legal system is classical way for graphene oxide, the graphene oxide reliable in quality of preparation.
Step S200: with the first electrode for work electrode, adopts the mixed liquor of three-electrode system to monomer and graphene oxide to carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load conducting polymer is modified.
Conducting polymer has electron conjugated structure, and its good stability, pliability are good, electric conductivity is adjustable and low cost and other advantages.Step S200 is in cyclic voltammetry scan, and scanning current potential reaches the reduction potential of graphene oxide, and graphene oxide generation electroreduction obtains redox graphene; Then scan oxidizing potential that current potential reaches monomer polymerization to carry out monomer polymerization and obtain conducting polymer, the electrode that the redox graphene composite material that finally repeatedly cyclic voltammetry scan obtains load conducting polymer is modified.
Wherein in an embodiment, the first electrode is any one in glass-carbon electrode, graphite electrode, carbon fiber electrode, carbon cloth electrode and carbon paste electrode.
Preferably, the first electrode is glass-carbon electrode.Wherein in an embodiment, glass-carbon electrode is carried out polishing with alumina powder on polishing cloth, clean for subsequent use in ultrasonic cleaner with absolute ethyl alcohol and water successively.
Wherein in an embodiment, the concrete steps of step S200 are: be added drop-wise on the first electrode by the mixed liquor of monomer and graphene oxide, dry, again with the first electrode be work electrode, to electrode be platinum plate electrode, reference electrode is for saturated calomel electrode, be placed in electrolyte solution and carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load conducting polymer is modified.
Wherein, wherein in an embodiment, the electrolyte solution in step S200 is sulfuric acid solution.The concentration of preferred sulfuric acid solution is 0.1mol/L.
In another embodiment, the concrete steps of step S200 are: with the first electrode be work electrode, to electrode be platinum plate electrode, reference electrode is for saturated calomel electrode, the mixed liquor being placed in monomer and graphene oxide carries out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load conducting polymer is modified.
Wherein in an embodiment, with the first electrode for work electrode, the scanning current potential adopting the mixed liquor of three-electrode system to monomer and graphene oxide to carry out cyclic voltammetry scan is-1.0V to 0.85V, and sweep speed is 20-100mV/s.Preferably, sweep speed is 50mV/s.
Step S300: the electrode modified with the redox graphene composite material of load conducting polymer is for work electrode, thiol solution is electrolyte, three-electrode system is adopted to carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load sulfhydrylation conducting polymer is modified.
Wherein in an embodiment, in the step of step S300: be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, thiol solution is the mixed solution of mercaptan in mixed solvent, and wherein mercaptan is DMcT (2,5-Dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazoles), the concentration of DMcT is 0.01-0.5mg/mL, and mixed solvent volume ratio is the absolute ethyl alcohol of 1:1 and the mixed liquor of 0.2mol/L sulfuric acid.Preferably, the concentration of DMcT is 0.05mg/mL.
Adopt the auxiliary mercaptan of electricity and conducting polymer to interact, obtain the conducting polymer composite material of sulfhydrylation, the conducting polymer composite material of sulfhydrylation is conducive to dispersion and the in-situ reducing of metallic.Concrete, the electrode that the redox graphene composite material obtaining load sulfhydrylation conducting polymer is modified.Class alkene electron conjugated structure as the sulfydryl of DMcT and the oxidation state polyaniline of polyaniline/redox graphene composite material interacts, and obtains the polyaniline/redox graphene composite material of sulfhydrylation.
Wherein in an embodiment, the electrode modified with the redox graphene composite material of load conducting polymer is for work electrode, thiol solution is electrolyte, and the scanning current potential adopting three-electrode system to carry out cyclic voltammetry scan is-0.2V to 0.8V, and sweep speed is 20-100mV/s.Preferably, sweep speed is 50mV/s.
Step S400: the electrode modified with the redox graphene composite material of load sulfhydrylation conducting polymer is for work electrode, metal salt solution is electrolyte, adopt three-electrode system to carry out constant potential reduction, obtain Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
Wherein, the conducting polymer composite material of sulfhydrylation, as carrier, makes slaine in-situ reducing on carrier simultaneously, utilizes the conducting polymer composite material of sulfhydrylation to improve dispersiveness and the stability of metallic.
Wherein, Electro Catalysts for Direct Methanol Fuel Cells is the redox graphene composite material of the sulfhydrylation conducting polymer of carrying metal particles, and its metallic particles dispersiveness is high and particle diameter is little.Metallic particles is nano particle, and granular size is 80-100nm.
Wherein in an embodiment, in the step of step S400: be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and the metal salt solution as electrolyte is the mixed solution of sulfuric acid, ethylene glycol and chloroplatinate or the mixed solution for sulfuric acid, ethylene glycol, chloroplatinate and ruthenium trichloride.Wherein, ethylene glycol can accelerate the reduction of slaine, and the metallic reunion in the reaction that reduction can also be suppressed to obtain as a kind of stabilizer is grown up.
Preferably, the concentration of sulfuric acid is 0.25mol/L, and the concentration of ethylene glycol is 0.5mol/L, and the concentration of chloroplatinate is 1-50mmol/L, and the concentration of ruthenium trichloride is 1-50mmol/L.Preferably, chloroplatinate is platinic sodium chloride or potassium chloroplatinate.
Wherein in an embodiment, the electrode modified with the redox graphene composite material of load sulfhydrylation conducting polymer is for work electrode, metal salt solution is electrolyte, and the current potential adopting three-electrode system to carry out constant potential reduction is-0.7 to-0.3V, and electrolysis time is 30-200s.Preferably, the current potential adopting three-electrode system to carry out constant potential reduction is-0.45V.
Wherein in an embodiment, on the work electrode that can obtain after the reaction step S400, scraping obtains Electro Catalysts for Direct Methanol Fuel Cells.
The preparation method of above-mentioned Electro Catalysts for Direct Methanol Fuel Cells, electrochemical method is adopted to make monomer oxidation and reduced by graphene oxide, make conducting polymer sulfhydrylation, and on the conducting polymer-redox graphene composite material of sulfhydrylation original position electroreduction slaine, operating procedure is simple, efficiency is high, environmental protection, the Electro Catalysts for Direct Methanol Fuel Cells obtained is the conducting polymer composite material of the sulfhydrylation of carrying metal particles, improve dispersiveness and the stability of metallic, its metallic particles dispersiveness is high, particle diameter is little is 80-100nm, can be used for direct methanol fuel cell, and there is high electroactive and high stability, the oxidation current of catalysis methanol reaches 22mA mg
pt -1.
It is below specific embodiment.
Embodiment 1
Aniline is distilled under the condition of heating and nitrogen protection, then continues to distill to the cut that obtains, until cut is colourless, keep in Dark Place in 4 DEG C for subsequent use.
Graphene oxide being dispersed in pH value is in the HAc-NaAc cushioning liquid of 4, and the concentration of graphene oxide in HAc-NaAc cushioning liquid is 1mg/mL.Add aniline again, obtain the graphene oxide dispersion of aniline, wherein the concentration of aniline is 0.01mol/L.
Take glass-carbon electrode as work electrode, the graphene oxide dispersion of aniline is added drop-wise on glass-carbon electrode, dry, again with the glass-carbon electrode modified be work electrode, to electrode be platinum plate electrode, reference electrode is for saturated calomel electrode, the sulfuric acid solution being placed in 0.1mol/L carries out cyclic voltammetry scan, scanning current potential be-1.0V to 0.85V, sweep speed is 50mV/s, obtain load polyaniline redox graphene composite material modification electrode.
The electrode modified with the redox graphene composite material of load polyaniline is for work electrode, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, electrolyte is thiol solution, carry out cyclic voltammetry scan, scanning current potential is that-0.2V is to 0.8V, sweep speed is 50mV/s, the electrode that the redox graphene composite material obtaining load sulfhydrylation polyaniline is modified, wherein thiol solution is the mixed solution of mercaptan in mixed solvent, wherein mercaptan is DMcT, the concentration of DMcT is 0.05mg/mL, mixed solvent is volume ratio is the absolute ethyl alcohol of 1:1 and the mixed liquor of 0.2mol/L sulfuric acid.
The electrode modified with the redox graphene composite material of load sulfhydrylation polyaniline is for work electrode, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, electrolyte is metal salt solution, wherein electrolyte is the mixed solution of sulfuric acid, ethylene glycol and platinic sodium chloride, the concentration of sulfuric acid is 0.25mol/L, the concentration of ethylene glycol is 0.5mol/L, the concentration of platinic sodium chloride is 50mmol/L, carry out constant potential reduction, the current potential of constant potential reduction is-0.45V, and electrolysis time is 30s, obtains Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
Embodiment 2
Embodiment 2 and the difference of embodiment 1 are that the concentration of aniline be the pH value of 0.1mol/L, HAc-NaAc cushioning liquid is 5, take graphite electrode as work electrode.Thiol solution is the mixed solution of mercaptan in mixed solvent, and wherein mercaptan is the concentration of DMcT, DMcT is 0.01mg/mL.
The electrode modified with the redox graphene composite material of load sulfhydrylation polyaniline is for work electrode, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, electrolyte is metal salt solution, wherein electrolyte is the mixed solution of sulfuric acid, ethylene glycol and potassium chloroplatinate, the concentration of sulfuric acid is 0.25mol/L, the concentration of ethylene glycol is 0.5mol/L, the concentration of potassium chloroplatinate is 1mmol/L, carry out constant potential reduction, the current potential of constant potential reduction is-0.3V, and electrolysis time is 100s, obtains Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1, and the concentration of aniline is the pH value of 0.05mol/L, HAc-NaAc cushioning liquid is 6, with carbon fiber electrically very work electrode.Thiol solution is the mixed solution of mercaptan in mixed solvent, and wherein mercaptan is the concentration of DMcT, DMcT is 0.5mg/mL.
The electrode modified with the redox graphene composite material of load sulfhydrylation polyaniline is for work electrode, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, electrolyte is metal salt solution, wherein electrolyte is the mixed solution of sulfuric acid, ethylene glycol and platinic sodium chloride, the concentration of sulfuric acid is 0.25mol/L, the concentration of ethylene glycol is 0.5mol/L, the concentration of platinic sodium chloride is 1mmol/L, carry out constant potential reduction, the current potential of constant potential reduction is-0.45V, and electrolysis time is 200s, obtains Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
Embodiment 4
Embodiment 4 is with the difference of embodiment 1, and monomer is pyrroles, and the concentration of pyrroles is the pH value of 0.1mol/L, HAc-NaAc cushioning liquid is 4, take carbon cloth electrode as work electrode.Thiol solution is the mixed solution of mercaptan in mixed solvent, and wherein mercaptan is the concentration of DMcT, DMcT is 0.2mg/mL.
The electrode modified with the redox graphene composite material of load sulfhydrylation polypyrrole is for work electrode, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, electrolyte is metal salt solution, wherein electrolyte is sulfuric acid, ethylene glycol, the mixed solution of platinic sodium chloride and ruthenium trichloride, the concentration of sulfuric acid is 0.25mol/L, the concentration of ethylene glycol is 0.5mol/L, the concentration of platinic sodium chloride is 50mmol/L, the concentration of ruthenium trichloride is 50mmol/L, carry out constant potential reduction, the current potential of constant potential reduction is-0.7V, electrolysis time is 120s, obtain Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
Embodiment 5
Embodiment 5 is with the difference of embodiment 1, and monomer is thiophene, and the concentration of thiophene is the pH value of 0.05mol/L, HAc-NaAc cushioning liquid is 5, take carbon paste electrode as work electrode.Thiol solution is the mixed solution of mercaptan in mixed solvent, and wherein mercaptan is the concentration of DMcT, DMcT is 0.05mg/mL.
The electrode modified with the redox graphene composite material of load sulfhydrylation polythiophene is for work electrode, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, electrolyte is metal salt solution, wherein electrolyte is sulfuric acid, ethylene glycol, the mixed solution of platinic sodium chloride and ruthenium trichloride, the concentration of sulfuric acid is 0.25mol/L, the concentration of ethylene glycol is 0.5mol/L, the concentration of platinic sodium chloride is 50mmol/L, the concentration of ruthenium trichloride is 50mmol/L, carry out constant potential reduction, the current potential of constant potential reduction is-0.45V, electrolysis time is 120s, obtain Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
The Electro Catalysts for Direct Methanol Fuel Cells that embodiment 1 obtains is made sem test, obtains scanning electron microscope (SEM) photograph as shown in Figure 2.As shown in Figure 2, in Electro Catalysts for Direct Methanol Fuel Cells sulfhydrylation polyaniline/redox graphene on the platinum grain dispersiveness of load high, and the particle diameter of platinum grain is little, and the size of particle is 80-100nm.
The Electro Catalysts for Direct Methanol Fuel Cells that embodiment 1 obtains is done electrocatalysis characteristic test.Adopt the three-electrode system of electrochemical workstation, be wherein platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and work electrode is the electrode of the Electro Catalysts for Direct Methanol Fuel Cells adopting embodiment 1 to obtain.Electrolytic solution used is the mixed solution of 1mol/L methyl alcohol and 0.5mol/L sulfuric acid, scanning potential region be-0.1V to 1.0V, sweep speed be 50mV/s, the cyclic voltammogram obtained is as shown in Figure 3, as shown in Figure 3, the oxidation current of Electro Catalysts for Direct Methanol Fuel Cells catalysis methanol reaches 22mA mg
pt -1(oxidation current that 1mg Electro Catalysts for Direct Methanol Fuel Cells is corresponding), illustrates that Electro Catalysts for Direct Methanol Fuel Cells has high electroactive and high stability.
Each technical characteristic of the above embodiment can combine arbitrarily, for making description succinct, the all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics does not exist contradiction, be all considered to be the scope that this specification is recorded.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for Electro Catalysts for Direct Methanol Fuel Cells, is characterized in that, comprises step:
By graphene oxide and monomer dispersion in HAc-NaAc cushioning liquid, obtain the mixed liquor of monomer and graphene oxide;
With the first electrode for work electrode, the mixed liquor of three-electrode system to described monomer and graphene oxide is adopted to carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load conducting polymer is modified;
The electrode modified with the redox graphene composite material of described load conducting polymer is for work electrode, thiol solution is electrolyte, three-electrode system is adopted to carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining load sulfhydrylation conducting polymer is modified; And
The electrode modified with the redox graphene composite material of described load sulfhydrylation conducting polymer is for work electrode, precious metal salt solution is electrolyte, adopt three-electrode system to carry out constant potential reduction, obtain described Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s.
2. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, is characterized in that, the pH value of described HAc-NaAc cushioning liquid is 4-6.
3. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, it is characterized in that, described first electrode is any one in glass-carbon electrode, graphite electrode, carbon fiber electrode, carbon cloth electrode and carbon paste electrode, and described monomer is any one in aniline, pyrroles and thiophene.
4. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, it is characterized in that, described with the first electrode for work electrode, adopt the mixed liquor of three-electrode system to described monomer and graphene oxide to carry out cyclic voltammetry scan, the concrete steps of the electrode that the redox graphene composite material obtaining load conducting polymer is modified are:
The mixed liquor of described monomer and graphene oxide is added drop-wise on described first electrode, dry, again with described first electrode be work electrode, to electrode be platinum plate electrode, reference electrode is for saturated calomel electrode, be placed in electrolyte solution and carry out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining described load conducting polymer is modified.
5. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, it is characterized in that, described with the first electrode for work electrode, adopt the mixed liquor of three-electrode system to described monomer and graphene oxide to carry out cyclic voltammetry scan, the concrete steps of the electrode that the redox graphene composite material obtaining load conducting polymer is modified are:
With the first electrode be work electrode, to electrode be platinum plate electrode, reference electrode is for saturated calomel electrode, the mixed liquor being placed in described monomer and graphene oxide carries out cyclic voltammetry scan, the electrode that the redox graphene composite material obtaining described load conducting polymer is modified.
6. the preparation method of the Electro Catalysts for Direct Methanol Fuel Cells according to claim 4 or 5, it is characterized in that, described with the first electrode for work electrode, the scanning current potential adopting the mixed liquor of three-electrode system to described monomer and graphene oxide to carry out cyclic voltammetry scan is-1.0 V to 0.85 V, and sweep speed is 20-100mV/s.
7. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, it is characterized in that, the described electrode modified with the redox graphene composite material of load conducting polymer is for work electrode, thiol solution is electrolyte, three-electrode system is adopted to carry out cyclic voltammetry scan, in the step of the electrode that the redox graphene composite material obtaining load sulfhydrylation conducting polymer is modified:
Be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and described thiol solution is the mixed solution of mercaptan in mixed solvent, and wherein mercaptan is DMcT, the concentration of DMcT is 0.01-0.5 mg/mL, and mixed solvent is volume ratio is the absolute ethyl alcohol of 1:1 and the mixed liquor of 0.2mol/L sulfuric acid.
8. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, it is characterized in that, the described electrode modified with the redox graphene composite material of load conducting polymer is for work electrode, thiol solution is electrolyte, the scanning current potential adopting three-electrode system to carry out cyclic voltammetry scan is-0.2V to 0.8V, and sweep speed is 20-100mV/s.
9. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, it is characterized in that, the described electrode modified with the redox graphene composite material of load sulfhydrylation conducting polymer is for work electrode, metal salt solution is electrolyte, adopt three-electrode system to carry out constant potential reduction, obtain in the step of described Electro Catalysts for Direct Methanol Fuel Cells on the working electrode (s:
Be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and described metal salt solution is the mixed solution of sulfuric acid, ethylene glycol and chloroplatinate or the mixed solution for sulfuric acid, ethylene glycol, chloroplatinate and ruthenium trichloride.
10. the preparation method of Electro Catalysts for Direct Methanol Fuel Cells according to claim 1, it is characterized in that, the described electrode modified with the redox graphene composite material of load sulfhydrylation conducting polymer is for work electrode, metal salt solution is electrolyte, the current potential adopting three-electrode system to carry out constant potential reduction is-0.7 to-0.3V, and electrolysis time is 30-200s.
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| CN108767210A (en) * | 2018-04-27 | 2018-11-06 | 西安理工大学 | A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate |
| CN108956730A (en) * | 2018-08-08 | 2018-12-07 | 甘肃省食品检验研究院 | A kind of electrochemical sensor and its preparation method and application for direct alcohol fuel cell |
| CN113611875A (en) * | 2021-08-05 | 2021-11-05 | 中汽创智科技有限公司 | Composite catalyst and preparation method and application thereof |
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| CN102220597A (en) * | 2011-05-20 | 2011-10-19 | 湖南大学 | Preparation method of conducting polymer-graphene composition |
| CN102361087A (en) * | 2011-10-27 | 2012-02-22 | 西北师范大学 | Graphene-polypyrrole/platinum nano modified glassy carbon electrode, preparation method for same and application thereof |
| CN103115952A (en) * | 2013-03-06 | 2013-05-22 | 西北师范大学 | Preparation method of mixed-thiol conductive polymer membrane-based modified electrode |
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| CN102220597A (en) * | 2011-05-20 | 2011-10-19 | 湖南大学 | Preparation method of conducting polymer-graphene composition |
| CN102361087A (en) * | 2011-10-27 | 2012-02-22 | 西北师范大学 | Graphene-polypyrrole/platinum nano modified glassy carbon electrode, preparation method for same and application thereof |
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| CN108767210A (en) * | 2018-04-27 | 2018-11-06 | 西安理工大学 | A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate |
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