CN102814177A - Preparation method of catalyst for direct methanol fuel cell and direct methanol fuel cell - Google Patents
Preparation method of catalyst for direct methanol fuel cell and direct methanol fuel cell Download PDFInfo
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- CN102814177A CN102814177A CN2012102925370A CN201210292537A CN102814177A CN 102814177 A CN102814177 A CN 102814177A CN 2012102925370 A CN2012102925370 A CN 2012102925370A CN 201210292537 A CN201210292537 A CN 201210292537A CN 102814177 A CN102814177 A CN 102814177A
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Abstract
The invention provides a preparation method of a catalyst for a direct methanol fuel cell. The preparation method comprises the following steps: a) conducting a redox reaction on a carbon substrate and potassium permanganate in water to obtain a carbon based catalyst carrier; and b) mixing and reacting the carbon based catalyst carrier obtained in the step a) with an active material precursor to obtain the catalyst for the direct methanol fuel cell. According to the method provided by the invention, the carbon substrate and potassium permanganate are used as raw materials, and treated with a one-pot reaction in water to obtain the carbon based catalyst carrier; and the obtained carbon based catalyst carrier does not need to be treated with complex post-treatment, and the active material can be deposited directly on the carbon based catalyst carrier to obtain the direct methanol fuel cell. The method provided by the invention is simple, easy to operate, and conducive to large-scale industrial production; and the obtained catalyst has high resistance to CO toxicity and high performance, and has better catalytic activity on methanol.
Description
Technical field
The present invention relates to the electro-catalysis technical field, relate in particular to a kind of Preparation of catalysts method and direct fuel methanol battery that is used for DMFC.
Background technology
DMFC is a kind of mutation in the Proton Exchange Membrane Fuel Cells; It directly uses methanol aqueous solution or steam methyl alcohol to supply with the source as fuel; With the air or oxygen is oxidant; Make chemical energy be converted into electric energy, and the reformation hydrogen production that need not pass through methyl alcohol, gasoline and natural gas is for generating.Methyl alcohol converts carbon dioxide, proton and electronics at anode; Proton Exchange Membrane Fuel Cells as standard is the same, and in negative electrode and oxygen reaction, electronics arrives negative electrode through external circuit to proton through PEM; And acting, thereby make chemical energy change into electric energy.DMFC is a kind of renewable and clean energy resource that chemical energy continuously is converted into electric energy; Have advantages such as volume is little, fuel is easy-to-use, theoretical energy conversion efficiency height, safe and convenient operation, lasting, the clean environmental protection of generating dutation, started quickly at low temperature, make it have very big potentiality aspect power supply of automobile and portable electron device.
It is fuel that DMFC adopts methyl alcohol, in the oxidization of methanol process, can generate multiple intermediate and accessory substance, takes off the various CO class species that proton forms like methyl alcohol; It is easy to by catalyst absorption, and is difficult to desorption, accumulates gradually at catalyst surface; Occupy the catalyst activity site, reduced the utilization rate of catalyst, even make serious poisoning of catalyst cause inefficacy; Hinder the further absorption of methyl alcohol and taken off proton reaction, cut off the continuity of reaction.The toxicity intermediate CO that methanol oxidation produced can cause the DMFC anode to produce higher overpotential.
For the catalytic activity that improves catalyst and the ability of anti-CO toxicity; Prior art with catalyst cupport on carrier; And it is modified, improve the ability of its supported catalyst, make the catalytic activity of catalyst and resisting CO poison performance all be enhanced.As disclosing a kind of method of the catalyst based carbon carrier of Pt being carried out modification in the prior art; This method is with the carrier of carbon black powder as catalyst; At first adopt the proton conductive polymer electrolyte; Be that perfluorinated sulfonic acid is modified carbon black powder, with the Pt-Ru catalyst of the carrier that obtains as DMFC.Its objective is the interfacial area that has prolonged between catalyst metals particle and the proton conductive medium, make the DMFC that obtains show superior performance, for the activity of such catalysts agent resisting CO poison performance (C.H.Park that all improves a lot; M.A.Scibioh, H.-J.Kim, I.-H.Oh; S.-A.Hong; H.Y.Ha.Journal of Power Sources, 2006,162:1023 ~ 1028.).But, in process to the modification of catalyst, need it carry out post processing to the catalyst carrier that obtains, i.e. heat treatment step, complicated operating process is unfavorable for extensive synthetic.
Summary of the invention
The object of the present invention is to provide a kind of Preparation of catalysts method that is used for DMFC; Method step provided by the invention is simple; Be beneficial to large-scale industrial production; And the catalyst that method provided by the invention obtains has advantages of high catalytic activity to methyl alcohol, has the ability of higher anti-CO toxicity.
The invention provides a kind of Preparation of catalysts method that is used for DMFC, may further comprise the steps:
A) carbon back material and potassium permanganate are carried out redox reaction in water, obtain the carbon-supported catalysts carrier;
B) the carbon-supported catalysts carrier and the active material presoma that said step a) are obtained mix, and obtain being used for the catalyst of DMFC after the reaction.
Preferably, said carbon back material is an active carbon, one or more in CNT and the Graphene.
Preferably, the mass ratio of carbon back material and said potassium permanganate is 80: (0.5 ~ 8).
Preferably, said water is the deionized water that resistivity is not less than 18.2M Ω cm.
Preferably, the time of said redox reaction is 1h ~ 10h.
Preferably, said active material presoma is a precious metal ion.
Preferably, said active material presoma is one or more in platinum ion, gold ion, ruthenium ion or the silver ion.
Preferably, the mass ratio of said carbon-supported catalysts carrier and said active material presoma is 1: (1 ~ 10).
Preferably, said step b) is specially:
B1) the carbon-supported catalysts carrier and the active material precursor solution that said step a) are obtained mix, and obtain mixed solution;
B2) add reducing agent in the mixed solution that said step b1) obtains, obtain being used for the catalyst of DMFC after the reaction.
The invention provides a kind of DMFC, comprise methyl alcohol anode, oxygen cathode, catalyst and PEM, it is characterized in that, said catalyst is the catalyst that is used for DMFC that the said preparation method of technique scheme obtains.
The present invention provides a kind of Preparation of catalysts method that is used for DMFC, may further comprise the steps: a) carbon back material and potassium permanganate are carried out redox reaction in water, obtain the carbon-supported catalysts carrier; B) the carbon-supported catalysts carrier and the active material presoma that said step a) are obtained mix, and obtain being used for the catalyst of DMFC after the reaction.The present invention is a raw material with carbon back material and potassium permanganate, at first prepares the carbon-supported catalysts carrier, then active material is deposited on the said carbon-supported catalysts carrier, can obtain being used for the catalyst of DMFC.Method provided by the invention after obtaining the carbon-supported catalysts carrier, need not it is carried out complicated post processing, directly in the reactant liquor with the adding of active material presoma, carries out the deposition of active material, obtains catalyst; And in method provided by the invention, carbon back material and potassium permanganate carry out one pot reaction at aqueous phase, can obtain the carbon-supported catalysts carrier.Method provided by the invention is simple, and easy operating is beneficial to and carries out large-scale industrial production.Preparation method provided by the invention obtains catalyst and has higher methyl alcohol electro catalytic activity and anti-CO poisoning capability, and a kind of preparing carriers method of simple and easy green is provided for the performance of DMFC.Experimental result shows that the electro-chemical activity surface area of the catalyst that method provided by the invention obtains is up to 102.90m
2/ g, the oxidation peak current potential of its CO that oxidation obtains to CO is negative to be moved, and promptly CO can be oxidized away by easier on catalyst provided by the invention, thereby can not influence the catalysis of catalyst to methanol oxidation; It is when the oxidation of catalysis methanol, and the oxidization of methanol spike potential is negative to be moved, and the electric current of oxidation peak is up to 682.73A/g.
Description of drawings
The XRD curve of the catalyst that Fig. 1 embodiment of the invention 1 and comparative example 1 obtain;
The XPS curve of the catalyst that Fig. 2 obtains for the embodiment of the invention 1 and comparative example 1;
The modified electrode that Fig. 3 processes for the catalyst that embodiment and comparative example obtain is at the H of deoxygenation
2SO
4In cyclic voltammetry curve;
The modified electrode that Fig. 4 processes for the catalyst of the embodiment of the invention 1 preparation is at H
2SO
4CO in the solution peels off curve and blank curve;
The H of modified electrode after deoxygenation that Fig. 5 processes for the catalyst that the embodiment of the invention and comparative example obtain
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH;
The modified electrode that the catalyst that Fig. 6 obtains for the embodiment of the invention 2 is processed is at H
2SO
4CO in the solution peels off curve and blank curve;
The modified electrode that the catalyst that Fig. 7 obtains for the embodiment of the invention 3 is processed is at H
2SO
4CO in the solution peels off curve and blank curve;
The modified electrode that the catalyst that Fig. 8 obtains for comparative example 2 of the present invention is processed is at H
2SO
4CO in the solution peels off curve and blank curve;
The modified electrode that the catalyst that Fig. 9 obtains for comparative example 1 of the present invention is processed is at H
2SO
4CO in the solution peels off curve and blank curve.
The specific embodiment
The present invention provides a kind of Preparation of catalysts method that is used for DMFC, may further comprise the steps:
A) carbon back material and potassium permanganate are carried out redox reaction in water, obtain the carbon-supported catalysts carrier;
B) the carbon-supported catalysts carrier and the active material presoma that said step a) are obtained mix, and obtain being used for the catalyst of DMFC after the reaction.
The present invention is a raw material with carbon back material and potassium permanganate at first, and it is carried out redox reaction at aqueous phase, has realized the modification to the carbon back material, obtains carbon back material catalyst carrier.
The present invention is preferred to be scattered in the carbon back material in the water earlier, obtains the suspension of carbon back material; And then in the suspension of said carbon back material, add potassium permanganate, and to carry out obtaining the carbon-supported catalysts carrier after the redox reaction, detailed process is following:
The present invention preferably at first is scattered in the carbon back material in the water, obtains the suspension of carbon back material.The present invention preferably under ultrasonic condition, is scattered in the carbon back material in the water, obtains the suspension of carbon back material.The present invention does not have special limitation to said ultrasonic condition like temperature, time etc., adopts ultrasonic technical scheme well known to those skilled in the art to get final product, until said carbon back material is uniformly dispersed in water.In the present invention; Said carbon back material is preferably one or more in active carbon, CNT and the Graphene, active carbon more preferably, and the present invention does not have special limitation to the source of carbon back material; The commercial goods of carbon back material can be adopted, also self-control carbon back material can be; The present invention does not have special limitation to the preparation method of said self-control carbon back material, adopts the technology of preparing scheme of carbon back material well known to those skilled in the art to get final product.Said water is preferably deionized water, and more preferably resistivity is not less than the deionized water of 18.2M Ω cm; The mass ratio of said carbon back material and said water is preferably 80: (150 ~ 500), more preferably 80: (180 ~ 300); The said ultrasonic time is preferably 1h ~ 5h, more preferably 1.5h ~ 3h.
After obtaining the suspension of carbon back material, the present invention adds potassium permanganate in the suspension of said carbon back material, carry out redox reaction after, obtain the carbon-supported catalysts carrier.The present invention is preferably under stirring condition; In the suspension of said carbon back material, add potassium permanganate, the present invention does not have special limitation to said stirring method, adopts the technical scheme of stirring well known to those skilled in the art to get final product; In the present invention; Said stirring can be manual stirring, also can be mechanical agitation, and said stirring is preferably magnetic agitation; The mass ratio of the described carbon back material of said potassium permanganate and technique scheme is preferably (0.5 ~ 8): 80, more preferably (1.2 ~ 5.4): 8; The time of said redox reaction is preferably 1 h ~ 10 hours, and more preferably 4 h ~ are 8 hours.
The present invention is a raw material with carbon back material and potassium permanganate; It is carried out one pot reaction at aqueous phase, can obtain the carbon-supported catalysts carrier, the preparation process to the carbon-supported catalysts carrier among the preparation method provided by the invention is simple; Easy operating is beneficial to the extensive synthetic of carbon-supported catalysts carrier.
After obtaining the carbon-supported catalysts carrier; The present invention mixes said carbon-supported catalysts carrier and active material presoma; Obtain being used for the catalyst of DMFC after the reaction, said catalyst comprises the carbon-supported catalysts carrier and is carried on the active material on the said carrier.In this process; Said active material is deposited on the said carbon-supported catalysts carrier; Realized the load to active material, the present invention does not have special limitation to the method for said deposition, and the technical scheme that adopts active material well known to those skilled in the art on catalyst carrier, to deposit gets final product.In the present invention, said active material presoma is preferably precious metal ion, more preferably one or more in platinum ion, gold ion, ruthenium ion or the silver ion, more preferably platinum ion; The mass ratio of said carbon-supported catalysts carrier and said active material presoma is preferably 1: (1 ~ 10), more preferably 1: (3 ~ 8).In the present invention, when said active material presoma is precious metal ion, said said carbon-supported catalysts carrier and active material presoma are mixed, the catalyst that obtains being used for DMFC after the reaction preferably specifically may further comprise the steps:
B1) the carbon-supported catalysts carrier and the active material precursor solution that said step a) are obtained mix, and obtain mixed solution;
B2) add reducing agent in the mixed solution that said step b1) obtains, obtain being used for the catalyst of DMFC after the reaction.
The solution of the preferred preparation earlier of the present invention active material presoma mixes said active material precursor solution then with institute carbon-supported catalysts carrier, obtain mixed solution.The present invention does not have special limitation to the compound method of said active material precursor solution, and the technical scheme that the active material precursor solution that adopts those skilled in the art to know is prepared gets final product.After obtaining the active material precursor solution; The carbon-supported catalysts carrier that the present invention need not that technique scheme is obtained carries out the post processing of load; Preferred directly said active material precursor solution is joined in the carbon-supported catalysts carrier that technique scheme obtains, obtain mixed solution.In the present invention, the mass concentration of said active material precursor solution is preferably (10 ~ 30) mg
Expensive Metal/ mL, more preferably (15 ~ 25) mg
Noble metal/ mL.When said active material presoma was platinum ion, said active material precursor solution was preferably platinum acid chloride solution; When said active material presoma was gold ion, said active material precursor solution was preferably chlorauric acid solution; When said active material presoma was silver ion, said active material precursor solution was preferably silver nitrate.With said active material precursor solution with after said carbon-supported catalysts carrier mixes; The present invention preferably stirs it; Obtain mixed solution, the present invention does not have particular restriction to said stirring method, adopts the technical scheme of stirring well known to those skilled in the art to get final product.In the present invention, can adopt the mode of manual stirring, also can adopt churned mechanically mode, the time of said stirring is preferably 1 h ~ 10 hours, and more preferably 3 h ~ are 6 hours.
After obtaining mixed solution, the present invention adds reducing agent in said mixed solution, and the active material simple substance that the reaction back forms is deposited on the said carbon-supported catalysts carrier, obtains being used for the catalyst of DMFC.The present invention preferably dropwise adds reducing agent in said mixed solution under stirring condition, said reducing agent is preferably NaBH
4, NaBH more preferably
4Solution, said NaBH
4The mass concentration of solution is preferably 0.1mg/mL ~ 5mg/mL, more preferably 1mg/mL ~ 3mg/mL.The present invention preferably carries out said reaction under stirring condition; In course of reaction, the active material presoma in the said mixed solution is reduced the agent reduction, obtains active material simple substance; Thereby make said active material be deposited on the said carbon-supported catalysts carrier, obtain catalyst.Said catalyst comprises the carbon-supported catalysts carrier and is carried on the active material on the said carrier.The mass ratio of said reducing agent and active material is preferably 2: (1 ~ 8), more preferably 2: (3 ~ 5); The time of said reaction is preferably 4h ~ 15h, more preferably 6h ~ 10h.
After reaction was accomplished, the present invention preferably carried out suction filtration and washing with the reactant liquor that obtains, and the present invention does not have special limitation to the method for said suction filtration and washing, adopts the technical scheme of suction filtration well known to those skilled in the art and washing to get final product.In the present invention, said washing is preferably and spends deionised water, and said deionized water is preferably the deionized water that resistivity is not less than 18.2M Ω cm, in filtrating, does not have Cl
-Exist; Then the solid that obtains is preferably carried out vacuum drying under 60 ℃ ~ 80 ℃, more preferably 65 ℃ ~ 75 ℃, obtain being used for the catalyst of methanol fuel cell.The present invention is to detecting Cl in the filtrating
-Method do not have special limitation, adopt detection Cl well known to those skilled in the art
-Method get final product.In the present invention, can in said filtrating, add liquor argenti nitratis ophthalmicus, not occur, then not have Cl in the explanation filtrating if there is deposition
-, this moment, washing was accomplished.
After grinding, the catalyst that is used for DMFC that the present invention will obtain carries out the X-ray diffraction test; Scanning angle is 10 ° ~ 90 °; Sweep speed is 5 °/min; Obtain the XRD figure spectrum of carrier composite catalyst, experimental result shows that the carbon-supported catalysts carrier of the Mn that mixed is for the not influence of accumulation mode of pt atom in the platinum that loads on carrier surface; The present invention carries out X-ray electron spectroscopy analysis after the carrier composite catalyst that obtains is ground, and obtains its XPS collection of illustrative plates, and experimental result shows that the introducing of Mn element does not cause tangible electronic effect.
The present invention will obtain is used for the catalysis that the DMFC catalyst is used for methyl alcohol, has tested its chemical property, and detailed process is following:
The present invention obtains modified electrode with the decorative material of the carrier composite catalyst that obtains as electrode, and as working electrode, the Ag/AgCl electrode as to electrode, places the three-electrode system that obtains the H of nitrogen deoxygenation as reference electrode, Pt sheet with modified electrode
2SO
4In the solution, carry out the cyclic voltammetry scan analysis, obtain modified electrode at H
2SO
4Cyclic voltammetry curve in the solution obtains the electro-chemical activity area of carrier composite catalyst provided by the invention through integral and calculating according to the cyclic voltammetry curve that obtains.Experimental result shows that the electro-chemical activity area of carrier composite catalyst provided by the invention is up to 102.90m
2/ g.
Preparation at modified electrode according to the invention is preferably carried out according to following method:
The catalyst that is used for DMFC provided by the invention is scattered in Nafion solution, obtains the dispersion liquid of catalyst;
Said dispersant liquid drop is applied on the glass-carbon electrode, obtains modified electrode after drying.
The present invention preferably under ultrasonic condition, is scattered in Nafion solution with the said catalyst that is used for DMFC, obtains the dispersion liquid of catalyst.In the present invention, the mass concentration of catalyst is preferably 1mg/ μ L ~ 8mg/ μ L in the catalyst dispersion liquid that obtains, and the said ultrasonic time is preferably 20min ~ 50min;
After obtaining dispersion liquid, the present invention is applied to said dispersant liquid drop on the glass-carbon electrode, obtains modified electrode after drying.Said in the present invention is applied to that the volume of dispersion liquid is preferably 3 μ L ~ 15 μ L on the glass-carbon electrode, more preferably 5 μ L ~ 10 μ L; The present invention does not have special limitation to the parameter of said glass-carbon electrode such as diameter etc., adopts glass-carbon electrode well known to those skilled in the art to get final product; Drip be coated with completion after, the present invention will be dripped has the glass-carbon electrode of dispersion liquid preferably at room temperature to dry, and obtains modified electrode, the present invention does not have special limitation to said method of drying, and can dry under field conditions (factors), can under infrared lamp, dry yet.
After obtaining modified electrode, the present invention is a working electrode with said modified electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as to electrode, obtain three-electrode system.It is the H of 0.5mol/L that the present invention preferably places the molar concentration of nitrogen deoxygenation with said three-electrode system
2SO
4In the solution; Carry out the cyclic voltammetry scan test; The present invention does not have special limitation to the method for said cyclic voltammetry scan, adopts the technical scheme of cyclic voltammetry scan well known to those skilled in the art to get final product, in the present invention; The speed of sweeping of said cyclic voltammetry scan is preferably 10mV/s ~ 100mV/s, more preferably 20mV/s ~ 80mV/s.
The present invention has detected the catalyst that is used for DMFC that the obtains anti-poisoning ability to intermediate oxidation product CO, and the present invention is with the described H of technique scheme
2SO
4Solution is for test end liquid, at said H
2SO
4Carry out the experiment of CO adsorption desorption in the solution, the present invention does not have special limitation to the method for said CO adsorption desorption, adopts the technical scheme of CO adsorption desorption well known to those skilled in the art to get final product.The present invention chooses double-deck district current potential to said H
2SO
4Behind the logical CO gas 15min, use high-purity N in the solution
2Remove the CO in the solution, carry out cyclic voltammetry scan in the solution after removing CO then, obtain the H behind the CO adsorption desorption
2SO
4The cyclic voltammogram of solution on modified electrode, experimental result show that catalyst provided by the invention is to the obvious suppression effect that is adsorbed with of CO; And the oxidation peak current potential of CO is negative moves; More help the oxidation of CO, this explanation, catalyst provided by the invention has the ability of higher anti-CO toxicity.
The catalyst that is used for DMFC that the present invention will obtain is used for the catalysis to methyl alcohol, and detailed process is following:
The three-electrode system that technique scheme is obtained places the H that contains methyl alcohol
2SO
4In the solution, carry out cyclic voltammetry scan, obtain the cyclic voltammetry curve of methyl alcohol on the modified electrode that catalyst is processed.
The present invention is in order to test the catalytic performance of said catalyst to methyl alcohol, and the three-electrode system that technique scheme is obtained places the H that contains methyl alcohol
2SO
4In the solution, carry out cyclic voltammetry scan, obtain the cyclic voltammetry curve of methyl alcohol on the modified electrode that catalyst is processed, can draw the catalytic performance of said catalyst methyl alcohol according to the cyclic voltammetry curve that obtains.In the present invention, the said H that contains methyl alcohol
2SO
4The molar concentration of methyl alcohol is preferably 0.1mol/L ~ 1.0mol/L in the solution, 0.5mol/L more preferably, H
2SO
4The molar concentration of solution is preferably 0.5mol/L; The present invention does not have special limitation to the parameter of said cyclic voltammetry scan like sweep speed etc., adopts the technical scheme of cyclic voltammetry scan well known to those skilled in the art to get final product.Experimental result shows that on the modified electrode that catalyst provided by the invention is processed, the oxidization of methanol spike potential is negative to be moved, and this explanation is easier to oxidization of methanol; The oxidization of methanol peak current increases, this explanation, and the catalyst that is used for DMFC provided by the invention has good catalytic performance to oxidization of methanol.
The invention provides a kind of DMFC, comprise methyl alcohol anode, oxygen cathode, catalyst and PEM, it is characterized in that, said catalyst is the catalyst that is used for DMFC that the said preparation method of technique scheme obtains.The present invention does not have special limitation to other parts and the annexation thereof of said DMFC except that catalyst; Adopt the structure of DMFC well known to those skilled in the art to get final product, as long as the catalyst that is used for DMFC that wherein used catalyst adopts preparation method provided by the invention to obtain.
The present invention provides a kind of Preparation of catalysts method that is used for DMFC, may further comprise the steps: a) carbon back material and potassium permanganate are carried out redox reaction in water, obtain the carbon-supported catalysts carrier; B) the carbon-supported catalysts carrier and the active material presoma that said step a) are obtained mix, and obtain being used for the catalyst of DMFC after the reaction.Preparation method provided by the invention is a raw material with carbon back material and potassium permanganate, it is carried out one pot reaction at aqueous phase can obtain the carbon-supported catalysts carrier.Need not then said carbon-supported catalysts carrier is carried out complicated post processing, directly on the carbon-supported catalysts carrier that obtains, deposit said active material, the catalyst that is used for DMFC that can obtain after the reaction; And in method provided by the invention, said carbon back material and said potassium permanganate carry out one pot reaction at aqueous phase, can obtain the carbon-supported catalysts carrier.Method provided by the invention need not the carbon-supported catalysts carrier that obtains is carried out the post processing of load, and method is simple, and easy operating is beneficial to large-scale industrial production.Preparation method provided by the invention obtains catalyst and has higher methyl alcohol electro catalytic activity and anti-CO poisoning capability, and a kind of preparing carriers method of simple and easy green is provided for the performance of DMFC.Experimental result shows that the electro-chemical activity surface area of the catalyst that method provided by the invention obtains is up to 102.90m
2/ g, the oxidation peak current potential of its CO that oxidation obtains to CO is negative to be moved, and promptly CO can be oxidized away by easier on catalyst provided by the invention, thereby can not influence the catalysis of catalyst to methanol oxidation; It is when the oxidation of catalysis methanol, and the oxidization of methanol spike potential is negative to be moved, and the electric current of oxidation peak is up to 682.73A/g.
In order to further specify the present invention, below in conjunction with embodiment the preparation method of a kind of carbon-supported catalysts carrier provided by the invention and the preparation method of carrier composite catalyst are elaborated, but can not they be interpreted as the qualification to protection domain of the present invention.
The conductive black 80mg that with model is Vulcan XC-72R is scattered in the 200mL deionized water through ultrasonic; Obtain the dispersion liquid of conductive black; Said deionization resistivity of water is 18.2M Ω cm, under magnetic agitation, in said conductive black, adds 1.4mg KMnO
4, stir reaction 6h down, obtain the carbon-supported catalysts carrier.
After above-mentioned reaction was accomplished, in the reactant liquor that obtains, adding the 1.105mL mass concentration was the 18.105mgPt/mL chloroplatinic acid aqueous solution, at room temperature stir 4 hours after, dropwise to wherein dripping the NaBH that mass concentration is 1mg/mL
4Solution carries out suction filtration with the reactant liquor that obtains after continuing to stir 5h, and spends deionised water, and said deionization resistivity of water is 18.2M Ω cm, and suction filtration is to there not being Cl
-Exist, the solid of inciting somebody to action at last obtains the carbon-supported catalysts carrier of platinum 80 ℃ of following vacuum drying, promptly is used for the catalyst of DMFC.
The present invention carries out the X-ray diffraction scanning analysis after the catalyst that obtains is ground, and scanning angle is 10 ° ~ 90 °, and sweeping speed is 5 °/min; The result is as shown in Figure 1, the XRD curve of the catalyst that Fig. 1 obtains for the embodiment of the invention 1 and comparative example 1, wherein; The XRD curve of the catalyst that obtains for the embodiment of the invention 1 of curve 1 wherein; The XRD curve of the catalyst that curve 2 obtains for comparative example 1 can be found out through curve in the comparison diagram 21 and curve 2, in the catalyst carrier provided by the invention; The doping of Mn is for the not influence of accumulation mode of Pt atom in the Pt nano particle that loads on carrier surface; That is to say that the carbon-supported catalysts carrier that the present invention obtains is when carrying active substance, the doping of Mn can not impact the performance of catalyst.
The present invention carries out the test of x-ray photoelectron power spectrum after the catalyst that obtains is ground; The result is as shown in Figure 2; The XPS curve of the catalyst that Fig. 2 obtains for the embodiment of the invention 1 and comparative example 1, the XPS curve of the catalyst that obtains for embodiment 1 of curve 1 wherein, the XPS curve of the catalyst that curve 2 obtains for comparative example 1; Can find out through curve in the comparison diagram 21 and curve 2; The introducing of the Mn element in the carbon-supported catalysts carrier provided by the invention does not cause tangible electronic effect, that is to say, carbon-supported catalysts carrier provided by the invention is in carrying active substance; The influence that the introducing of Mn element can not cause the electronic effect of catalyst, thus just can not impact its catalytic performance yet.
The catalyst that the 5mg present embodiment is obtained joins ultrasonic dispersion 30min in the 50 μ L Nafion solution, obtains the dispersion soln of catalyst; The dispersion soln of the said catalyst of 10 μ L dripped be applied on the glass-carbon electrode, at room temperature dry, obtain modified electrode.
With said modified electrode is working electrode, and the Ag/AgCl electrode as to electrode, utilizes three-electrode system with the Pt sheet as reference electrode, is the H of 0.5mol/L in the molar concentration of nitrogen deoxygenation
2SO
4In carry out cyclic voltammetry scan, sweep speed for 20mV/s, the result is as shown in Figure 3, the modified electrode that Fig. 3 processes for the catalyst that embodiment and comparative example obtain is at the H of deoxygenation
2SO
4In cyclic voltammetry curve, wherein the modified electrode processed of the catalyst that obtains for embodiment 1 of curve 1 is at the H of deoxygenation
2SO
4In cyclic voltammetry curve, through calculating the electro-chemical activity area of the catalyst that obtains the present embodiment preparation, the result is as shown in table 1 by the curve among Fig. 31, the The performance test results of the catalyst that table 1 obtains for the embodiment of the invention and comparative example.
The present invention investigates the electro-chemical activity area of catalyst provided by the invention and the ability of its anti-CO toxicity through the experiment of CO adsorption desorption.The present invention is at above-mentioned H
2SO
4In the solution, carry out the experiment of CO adsorption desorption, choose and use high-purity N after double-deck district current potential leads to CO gas 15min
2Remove the CO in the solution, and then carry out cyclic voltammetry scan, the scanning number of turns is 2 circles, and the result is as shown in Figure 4, and the modified electrode that Fig. 4 processes for the embodiment of the invention 1 preparation catalyst is at H
2SO
4CO in the solution peels off curve and blank curve, can draw the CO adsorption desorption active surface area of catalyst by Fig. 4, and the result is as shown in table 1, the characterization result of the catalyst performance that table 1 obtains for the embodiment of the invention and comparative example.And can find out that through comparison diagram 9 on the modified electrode that the catalyst of present embodiment preparation is processed, the oxidation peak current potential of CO is negative to be moved, CO is oxidized more easily on the electrode that catalyst provided by the invention is modified in this explanation, thereby has reduced its poisoning effect.
The present invention has investigated the catalytic capability of catalyst to methyl alcohol, adopts above-mentioned three-electrode system, and the molar concentration after the nitrogen deoxygenation is the H of 0.5mol/L
2SO
4With molar concentration be the CH of 0.5mol/L
3Carry out cyclic voltammetry scan in the mixed solution of OH, the result is as shown in Figure 5, the H of modified electrode after deoxygenation that Fig. 5 processes for the catalyst that the embodiment of the invention and comparative example obtain
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the wherein H of modified electrode after deoxygenation that process of the catalyst that obtains for embodiment 1 of curve 1
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the H of modified electrode after deoxygenation that the catalyst that curve 4 obtains for comparative example 1 of the present invention is processed
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH; Can find out through curve in the comparison diagram 51 and curve 4; The modified electrode that catalyst provided by the invention obtains is when catalysis methanol, and the oxidization of methanol current potential reduces, and oxidation current is improved; This explanation, catalyst provided by the invention has the performance of higher catalysis methanol.
With the 80mg model is conductive black and the 2.7mg KMnO of Vulcan XC-72R
4Be raw material, obtain the carbon-supported catalysts carrier,, obtain being used for the catalyst of DMFC according to embodiment 1 described method deposited catalyst platinum on said carbon-supported catalysts carrier according to embodiment 1 described method.The 5mg catalyst that obtains is joined ultrasonic dispersion 30min in 50 μ L Nafion solution, the 1mL ethanol, obtain the dispersion soln of catalyst; The dispersion soln of the said catalyst of 10 μ L dripped be applied on the glass-carbon electrode, at room temperature dry, obtain modified electrode.
With said modified electrode is working electrode, and the Ag/AgCl electrode as to electrode, utilizes three-electrode system with the Pt sheet as reference electrode, is the H of 0.5mol/L in the molar concentration of nitrogen deoxygenation
2SO
4In carry out cyclic voltammetry scan, sweep speed for 20mV/s, the result is as shown in Figure 3, the modified electrode that Fig. 3 processes for the catalyst that embodiment and comparative example obtain is at the H of deoxygenation
2SO
4In cyclic voltammetry curve.Wherein the modified electrode processed of the catalyst that obtains for embodiment 2 of curve 2 is at the H of deoxygenation
2SO
4In cyclic voltammetry curve, through calculating the electro-chemical activity area of the catalyst that obtains the present embodiment preparation, the result is as shown in table 1 by the curve among Fig. 32, the The performance test results of the catalyst that table 1 obtains for the embodiment of the invention and comparative example.
The present invention takes off adsorption process according to the CO described in the embodiment 1, investigated electroactive area and the ability of its anti-CO toxicity of the catalyst of present embodiment preparation, and the result is as shown in Figure 6, and the modified electrode that Fig. 6 processes for the catalyst of the embodiment of the invention 2 preparations is at H
2SO
4CO in the solution peels off curve and curve, and wherein the modified electrode processed for the catalyst of the embodiment of the invention 2 preparations of curve 1 is at H
2SO
4CO in the solution peels off curve, and the modified electrode that the catalyst that curve 2 prepares for the embodiment of the invention 2 is processed is at H
2SO
4The blank curve of CO in the solution can draw CO adsorption desorption active surface area by Fig. 4, and the result is as shown in table 1, the characterization result of the catalyst performance that table 1 obtains for the embodiment of the invention and comparative example.And can find out that through comparison diagram 9 on the modified electrode that the catalyst of present embodiment preparation is processed, the oxidation peak current potential of CO is negative to be moved, CO is oxidized more easily on the electrode that catalyst provided by the invention is modified in this explanation, thereby has reduced its poisoning effect.
The present invention is according to embodiment 1 described process, investigated the catalytic capability of the catalyst of present embodiment preparation to methyl alcohol, the result shown in 5, the H of modified electrode after deoxygenation that Fig. 5 processes for the catalyst that the embodiment of the invention and comparative example obtain
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the wherein H of modified electrode after deoxygenation that process of the catalyst that obtains for embodiment 2 of curve 2
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the H of modified electrode after deoxygenation that the catalyst that curve 4 obtains for comparative example 1 of the present invention is processed
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH; Can find out through curve in the comparison diagram 52 and curve 4,, the modified electrode that catalyst provided by the invention obtains is when catalysis methanol; The oxidization of methanol current potential reduces; Oxidation current is improved, this explanation, and catalyst provided by the invention has the performance of higher catalysis methanol.
Embodiment 3
With the 80mg model is conductive black and the 5.4mg KMnO of Vulcan XC-72R
4Be raw material, obtain the carbon-supported catalysts carrier,, obtain being used for the catalyst of DMFC according to embodiment 1 described method deposited catalyst platinum on said carbon-supported catalysts carrier according to embodiment 1 described method.The 5mg catalyst that obtains is joined ultrasonic dispersion 30min in 50 μ L Nafion solution, the 1mL ethanol, obtain the dispersion soln of catalyst; The dispersion soln of the said catalyst of 10 μ L dripped be applied on the glass-carbon electrode, at room temperature dry, obtain modified electrode.
With said modified electrode is working electrode, and the Ag/AgCl electrode as to electrode, utilizes three-electrode system with the Pt sheet as reference electrode, is the H of 0.5mol/L in the molar concentration of nitrogen deoxygenation
2SO
4In carry out cyclic voltammetry scan, sweep speed for 20mV/s, the result is as shown in Figure 3, the modified electrode that Fig. 3 processes for the catalyst that embodiment and comparative example obtain is at the H of deoxygenation
2SO
4In cyclic voltammetry curve.Wherein the modified electrode processed of the catalyst that obtains for embodiment 2 of curve 2 is at the H of deoxygenation
2SO
4In cyclic voltammetry curve, through calculating the electro-chemical activity area of the catalyst that obtains the present embodiment preparation, the result is as shown in table 1 by the curve among Fig. 32, the The performance test results of the catalyst that table 1 obtains for the embodiment of the invention and comparative example.
The present invention is according to embodiment 1 described CO adsorption desorption process, investigated electroactive area and the ability of its anti-CO toxicity of the catalyst of present embodiment preparation, and the result is as shown in Figure 7, and the modified electrode that Fig. 7 processes for the catalyst of the embodiment of the invention 3 preparations is at H
2SO
4CO in the solution peels off curve and blank curve, and wherein the modified electrode processed for the catalyst of the embodiment of the invention 3 preparations of curve 1 is at H
2SO
4CO in the solution peels off curve, and the modified electrode that the catalyst that curve 2 prepares for the embodiment of the invention 3 is processed is at H
2SO
4The blank curve of CO in the solution can draw CO adsorption desorption active surface area by Fig. 7, and the result is as shown in table 1, the characterization result of the catalyst performance that table 1 obtains for the embodiment of the invention and comparative example.And can find out that through comparison diagram 9 on the modified electrode that the catalyst of present embodiment preparation is processed, the oxidation peak current potential of CO is negative to be moved, CO is oxidized more easily on the electrode that catalyst provided by the invention is modified in this explanation, thereby has reduced its poisoning effect.
The present invention is according to embodiment 1 described process, investigated the catalytic capability of the catalyst of present embodiment preparation to methyl alcohol, and the result is as shown in Figure 5, the H of modified electrode after deoxygenation that Fig. 5 processes for the catalyst that the embodiment of the invention and comparative example obtain
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the wherein H of modified electrode after deoxygenation that process of the catalyst that obtains for embodiment 3 of curve 3
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the H of modified electrode after deoxygenation that the catalyst that curve 4 obtains for comparative example 1 of the present invention is processed
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH; Can find out through curve in the comparison diagram 53 and curve 4; The modified electrode that catalyst provided by the invention obtains is when catalysis methanol, and the oxidization of methanol current potential reduces, and oxidation current is improved; This explanation, catalyst provided by the invention has the performance of higher catalysis methanol.
The carrier composite catalyst that obtains with embodiment 1 is as the catalyst in the DMFC, and itself and methyl alcohol, oxygen and PEM is compound, and the method according to the prior art for preparing DMFC prepares DMFC.
The present invention has investigated the performance of the DMFC that obtains, and the result shows, the catalyst that adopts preparation method of the present invention to obtain, and it has catalytic performance preferably to methyl alcohol, and has the ability of higher resisting CO poison.
Comparative example 1
The conductive black 80mg that with the model is Vulcan XC-72R adopts the method for embodiment 1 as catalyst carrier, prepares catalyst.
The present invention carries out the X-ray diffraction scanning analysis after the catalyst that obtains is ground, and scanning angle is 10 ° ~ 90 °, and sweeping speed is 5 °/min; The result is as shown in Figure 1, the XRD curve of the catalyst that Fig. 1 obtains for the embodiment of the invention 1 and comparative example 1, wherein; The XRD curve of the catalyst that curve 2 obtains for comparative example 1; Can find out that through curve in the comparison diagram 21 and curve 2 Mn in the catalyst carrier provided by the invention that is to say for the not influence of accumulation mode of the Pt atom in the Pt nano particle that loads on carrier surface; Carbon-supported catalysts carrier provided by the invention is when carrying active substance, and the doping of Mn can not impact the performance of catalyst.
The present invention carries out the test of x-ray photoelectron power spectrum after the catalyst that obtains is ground; The result is as shown in Figure 2, the XPS curve of the catalyst that Fig. 2 obtains for the embodiment of the invention 1 and comparative example 1, wherein the XPS curve of the catalyst that obtains for comparative example 1 of curve 2; Can find out through curve in the comparison diagram 21 and curve 2; The introducing of the Mn element in the carbon-supported catalysts carrier provided by the invention does not cause tangible electronic effect, that is to say, carbon-supported catalysts carrier provided by the invention is in carrying active substance; The introducing of Mn element can not impact the electronic effect of catalyst, thereby just can not impact its catalytic performance yet.
The 5mg catalyst that obtains is joined ultrasonic dispersion 30min in 50 μ L Nafion solution, the 1mL ethanol, obtain the dispersion soln of catalyst; The dispersion soln of the said catalyst of 10 μ L dripped be applied on the glass-carbon electrode, at room temperature dry, obtain modified electrode.
With said modified electrode is working electrode, and the Ag/AgCl electrode as to electrode, utilizes three-electrode system with the Pt sheet as reference electrode, is the H of 0.5mol/L in the molar concentration of nitrogen deoxygenation
2SO
4In carry out cyclic voltammetry scan, sweep speed for 20mV/s, the result is as shown in Figure 3, the modified electrode that Fig. 3 processes for the catalyst that embodiment and comparative example obtain is at the H of deoxygenation
2SO
4In cyclic voltammetry curve, wherein the modified electrode processed of the catalyst that obtains for comparative example 1 of curve 5 is at the H of deoxygenation
2SO
4In cyclic voltammetry curve, through calculating the electro-chemical activity area of the catalyst that obtains the preparation of this comparative example, the result is as shown in table 1 by the curve among Fig. 35, the The performance test results of the catalyst that table 1 obtains for the embodiment of the invention and comparative example.
The present invention takes off adsorption process according to the CO described in the embodiment 1; The electro-chemical activity area of the catalyst that comparative example of the present invention provides and the ability of its anti-CO toxicity have been investigated; The result is as shown in Figure 9, and the modified electrode that Fig. 9 processes for the catalyst of comparative example of the present invention 1 preparation is at H
2SO
4CO in the solution peels off curve and blank curve, and wherein the modified electrode processed for the catalyst of comparative example 1 preparation of the present invention of curve 1 is at H
2SO
4CO in the solution peels off curve, and the modified electrode that the catalyst that curve 2 prepares for comparative example of the present invention is processed is at H
2SO
4The blank curve of CO in the solution can obtain CO adsorption desorption active surface area by Fig. 9, and the result is as shown in table 1, the characterization result of the catalyst performance that table 1 obtains for the embodiment of the invention and comparative example.And through with Fig. 4, Fig. 6, Fig. 7 in curve contrast; On the modified electrode that the catalyst of embodiment of the invention preparation is processed; The oxidation peak current potential of CO is negative to be moved, and CO is oxidized more easily on the electrode that catalyst provided by the invention is modified in this explanation, thereby has reduced its poisoning effect.
The present invention is according to embodiment 1 described process, investigated the catalytic capability of the catalyst of this comparative example preparation to methyl alcohol, and the result is as shown in Figure 5, the H of modified electrode after deoxygenation that Fig. 5 processes for the catalyst that the embodiment of the invention and comparative example obtain
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the wherein H of modified electrode after deoxygenation that process of the catalyst that obtains for comparative example 1 of curve 5
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH; Through the curve among Fig. 55 is compared and can be found out with curve 3 with curve 1, curve 2; The modified electrode that catalyst provided by the invention obtains is when catalysis methanol, and the oxidization of methanol current potential reduces, and oxidation current is improved; This explanation, catalyst provided by the invention has the performance of higher catalysis methanol.
Comparative example 2
With the 80mg model is conductive black and the 8.1mg KMnO of Vulcan XC-72R
4Be raw material, obtain the carbon-supported catalysts carrier,, obtain being used for the catalyst of DMFC according to embodiment 1 described method deposited catalyst platinum on said carbon-supported catalysts carrier according to embodiment 1 described method.The 5mg catalyst that obtains is joined ultrasonic dispersion 30min in the 50 μ L Nafion solution, obtain the dispersion soln of catalyst; The dispersion soln of the said catalyst of 10 μ L dripped be applied on the glass-carbon electrode, at room temperature dry, obtain modified electrode.
The present invention takes off adsorption process according to the CO described in the embodiment 1, investigated electroactive area and the ability of its anti-CO toxicity of the catalyst of this comparative example preparation, and the result is as shown in Figure 8, and the modified electrode that Fig. 8 processes for the catalyst of comparative example 2 preparations of the present invention is at H
2SO
4CO in the solution peels off curve and blank curve, and wherein the modified electrode processed for the catalyst of comparative example 2 preparations of the present invention of curve 1 is at H
2SO
4CO in the solution peels off curve, and the modified electrode that the catalyst that curve 2 prepares for comparative example 2 of the present invention is processed is at H
2SO
4The blank curve of CO in the solution can obtain CO adsorption desorption active surface area by Fig. 8, and the result is as shown in table 1, the characterization result of the catalyst performance that table 1 obtains for the embodiment of the invention and comparative example.And through the curve in the comparison diagram 9, prepare on the modified electrode that catalyst processes at comparative example of the present invention, the oxidation peak current potential of CO is negative to be moved, and CO is oxidized more easily on the electrode that catalyst provided by the invention is modified in this explanation, thereby has reduced its poisoning effect.
The present invention is according to embodiment 1 described process, investigated the catalytic capability of the catalyst of present embodiment preparation to methyl alcohol, the result shown in 5, the H of modified electrode after deoxygenation that Fig. 5 processes for the catalyst that the embodiment of the invention and comparative example obtain
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the wherein H of modified electrode after deoxygenation that process of the catalyst that obtains for comparative example 2 of curve 5
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH, the H of modified electrode after deoxygenation that the catalyst that curve 4 obtains for comparative example 1 of the present invention is processed
2SO
4And CH
3Cyclic voltammetry curve in the mixed solution of OH; Can find out through curve in the comparison diagram 54 and curve 5; The modified electrode that the catalyst that comparative example 2 of the present invention provides obtains is when catalysis methanol, and the oxidization of methanol electric current is reduced, this explanation; In catalyst carrier provided by the invention, the ability of the catalyst methanol oxidation that the doping of too high Mn can cause obtaining reduces.
The experimental result that table 1 embodiment of the invention and comparative example obtain
Can find out that by table 1 hydrogen adsorption desorption active surface area, CO adsorption desorption active surface area appear with the raising of Mn doping and increase the trend that afterwards reduces earlier, but the sample of doped with Mn with respect to in the comparative example 1 for the inhibitory action significantly that is adsorbed with of CO.And the oxidation peak current potential of contrast CO, the sample that embodiment and comparative example 2 obtain all has comparative example 1 to bear in various degree and moves, and proves that Mn is doped with to be beneficial to the oxidation that poisons the centre species.And mixing of Mn makes that the oxidization of methanol spike potential is negative to be moved; Methanol oxidation is more prone to, and along with the increase of doping, peak point current also appears and increases earlier the trend that afterwards reduces; Promptly on doping, there are an optimal value, i.e. 5.4mg KMnO among the embodiment 3
2/ 80mgVulcan72R.
Can know that by above embodiment the present invention provides a kind of preparation method who is used for the carrier composite catalyst of DMFC, carbon back material and potassium permanganate are carried out redox reaction in water, obtain the carbon-supported catalysts carrier; On the carbon-supported catalysts carrier that obtains, deposit active material then, the catalyst that is used for DMFC that obtains after the reaction.The present invention has made the carbon-supported catalysts carrier through one pot reaction; And the carbon-supported catalysts carrier that obtains need not to carry out complicated post processing; Behind the carbon-supported catalysts carrier that obtains; Directly carry out the deposition of active material above that, can obtain being used for the catalyst of DMFC after the reaction.Method provided by the invention is simple, easy operating, and also the catalyst carrier that obtains has good performance.In preparation method provided by the invention; Pass through redox reaction; In the carbon-supported catalysts carrier that obtains, mixing of Mn being arranged, is 80 at the mass ratio of carbon back material and said potassium permanganate: between (0.5 ~ 8), along with the quality of potassium permanganate raises; The content of the Mn that mixes also just increases, and makes behind its supported catalyst all to be greatly improved to the mithridatism ability of CO with to the catalytic capability of methanol oxidation.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. Preparation of catalysts method that is used for DMFC may further comprise the steps:
A) carbon back material and potassium permanganate are carried out redox reaction in water, obtain the carbon-supported catalysts carrier;
B) the carbon-supported catalysts carrier and the active material presoma that said step a) are obtained mix, and obtain being used for the catalyst of DMFC after the reaction.
2. preparation method according to claim 1 is characterized in that, said carbon back material is one or more in active carbon, CNT and the Graphene.
3. preparation method according to claim 1 is characterized in that, the mass ratio of carbon back material and said potassium permanganate is 80: (0.5 ~ 8).
4. preparation method according to claim 1 is characterized in that, said water is the deionized water that resistivity is not less than 18.2M Ω cm.
5. preparation method according to claim 1 is characterized in that, the time of said redox reaction is 1h ~ 10h.
6. preparation method according to claim 1 is characterized in that, said active material presoma is a precious metal ion.
7. preparation method according to claim 1 is characterized in that, said active material presoma is one or more in platinum ion, gold ion, ruthenium ion or the silver ion.
8. preparation method according to claim 1 is characterized in that, the mass ratio of said carbon-supported catalysts carrier and said active material presoma is 1: (1 ~ 10).
9. preparation method according to claim 1 is characterized in that, said step b) is specially:
B1) the carbon-supported catalysts carrier and the active material precursor solution that said step a) are obtained mix, and obtain mixed solution;
B2) add reducing agent in the mixed solution that said step b1) obtains, obtain being used for the catalyst of DMFC after the reaction.
10. a DMFC comprises methyl alcohol anode, oxygen cathode, catalyst and PEM, it is characterized in that, said catalyst is the catalyst that is used for DMFC that the said preparation method of claim 1 ~ 9 obtains.
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| CN103212442A (en) * | 2013-04-14 | 2013-07-24 | 青岛大学 | Catalyst for catalyzing methyl alcohol, preparation method and chemically modified electrode of catalyst |
| CN105594047A (en) * | 2014-03-28 | 2016-05-18 | 恩亿凯嘉股份有限公司 | Production method for electrode catalyst, electrode catalyst, composition for forming gas diffusion electrode, gas diffusion electrode, membrane-electrode assembly (MEA), and fuel cell stack |
| CN111063900A (en) * | 2018-10-16 | 2020-04-24 | 天津工业大学 | KMnO4Preparation of Pd-Ni catalyst using modified carbon black as carrier |
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| CN111063900A (en) * | 2018-10-16 | 2020-04-24 | 天津工业大学 | KMnO4Preparation of Pd-Ni catalyst using modified carbon black as carrier |
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Effective date of registration: 20180321 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |