CN102814177B - 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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- CN102814177B CN102814177B CN201210292537.0A CN201210292537A CN102814177B CN 102814177 B CN102814177 B CN 102814177B CN 201210292537 A CN201210292537 A CN 201210292537A CN 102814177 B CN102814177 B CN 102814177B
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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 electro-catalysis technical field, particularly relate to a kind of preparation method and direct fuel methanolica cell of the catalyst for DMFC.
Background technology
DMFC is a kind of mutation in Proton Exchange Membrane Fuel Cells, it directly uses methanol aqueous solution or steam methane to be fuel supply source, take air or oxygen as oxidant, make chemical energy be converted into electric energy, and do not need by the reformation hydrogen production of methyl alcohol, gasoline and natural gas for generating.Methyl alcohol is converted to carbon dioxide, proton and electronics at anode, as the Proton Exchange Membrane Fuel Cells of standard, proton is reacted at negative electrode and oxygen by PEM, and electronics arrives negative electrode by external circuit, and doing work, thus chemical energy is become electric energy.DMFC is a kind of renewable and clean energy resource chemical energy being continuously converted into electric energy, there is the advantages such as volume is little, fuel is easy-to-use, theoretical energy transformation efficiency is high, lasting, the clean environmental protection of safe and convenient operation, generating dutation, started quickly at low temperature, make it in the power supply of automobile and portable electron device, have very large potentiality.
DMFC adopts methyl alcohol to be fuel, multiple intermediate and accessory substance can be generated in the oxidizing process of methyl alcohol, as methyl alcohol takes off the various CO class species of proton formation, it is easy to catalyzed dose of absorption, and is difficult to desorption, accumulate gradually at catalyst surface, occupy active catalyst sites, reduce the utilization rate of catalyst, even make that catalyst is seriously poisoning causes inefficacy, hinder the further absorption of methyl alcohol and de-proton reaction, cut off the continuity of reaction.The toxic intermediate CO that methanol oxidation produces can cause DMFC anode to produce higher overpotential.
In order to the ability of the catalytic activity and anti-CO toxicity that improve catalyst, prior art by catalyst cupport on carrier, and it is modified, improve the ability of its supported catalyst, the catalytic activity of catalyst and resisting CO poison performance are all enhanced.As disclosed a kind of method of the catalyst based carbon carrier of Pt being carried out to modification in prior art, the method is using carbon black powder as the carrier of catalyst, first proton conductive polymer electrolyte is adopted, namely perfluorinated sulfonic acid is modified carbon black powder, using the carrier that the obtains Pt-Ru catalyst as DMFC.Its objective is the interfacial area extended between catalyst metal particles and proton conductive medium, the DMFC obtained is made to show superior performance, activating agent resisting CO poison performance for catalyst all improves a lot (C.H.Park, 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 the process of the modification to catalyst, need to the catalyst carrier obtained that it carries out post processing, i.e. heat treatment step, operating process is complicated, is unfavorable for extensive synthesis.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the catalyst 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 higher catalytic activity to methyl alcohol, there is the ability of higher anti-CO toxicity.
The invention provides a kind of preparation method of the catalyst for DMFC, comprise the following steps:
A) carbon substrate and potassium permanganate are carried out redox reaction in water, obtain carbon based catalyst support;
B) carbon based catalyst support described step a) obtained and the mixing of active material presoma, obtain the catalyst for DMFC after reaction.
Preferably, described carbon substrate is active carbon, one or more in CNT and Graphene.
Preferably, the mass ratio of carbon substrate and described potassium permanganate is 80:(0.5 ~ 8).
Preferably, described water is the deionized water that resistivity is not less than 18.2M Ω cm.
Preferably, the time of described redox reaction is 1h ~ 10h.
Preferably, described active material presoma is precious metal ion.
Preferably, described active material presoma is one or more in platinum ion, gold ion, ruthenium ion or silver ion.
Preferably, the mass ratio of described carbon based catalyst support and described active material presoma is 1:(1 ~ 10).
Preferably, described step b) is specially:
B1) carbon based catalyst support described step a) obtained and the mixing of active material precursor solution, obtain mixed solution;
B2) described step b1) add reducing agent in the mixed solution that obtains, obtain the catalyst for DMFC after reaction.
The invention provides a kind of DMFC, comprise Methanol Anode, oxygen cathode, catalyst and PEM, it is characterized in that, the catalyst for DMFC that described catalyst obtains for preparation method described in technique scheme.
The invention provides a kind of preparation method of the catalyst for DMFC, comprise the following steps: a) carbon substrate and potassium permanganate are carried out redox reaction in water, obtain carbon based catalyst support; B) carbon based catalyst support described step a) obtained and the mixing of active material presoma, obtain the catalyst for DMFC after reaction.The present invention for raw material with carbon substrate and potassium permanganate, first prepares carbon based catalyst support, is then deposited on by active material on described carbon based catalyst support, can obtains the catalyst for DMFC.Method provided by the invention, after obtaining carbon based catalyst support, without the need to carrying out complicated post processing to it, in the reactant liquor directly added by active material presoma, carries out the deposition of active material, obtains catalyst; And in method provided by the invention, carbon substrate and potassium permanganate carry out one pot reaction in aqueous phase, can obtain carbon based catalyst support.Method provided by the invention is simple, is easy to operation, 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 CO tolerance catalysts ability, and the performance for DMFC provides a kind of support preparation method of simple and easy green.Experimental result shows, the electrochemical active surface of the catalyst that method provided by the invention obtains is up to 102.90m
2/ g, its oxidation peak current potential CO being oxidized to the CO obtained is born and is moved, and namely CO can be oxidized away by easier on catalyst provided by the invention, thus can not affect the catalysis of catalyst to methanol oxidation; It is when the oxidation of catalysis methanol, and the oxidation peak current potential of methyl alcohol is negative to be moved, and the electric current of oxidation peak is up to 682.73A/g.
Accompanying drawing explanation
The XRD curve of the catalyst that Fig. 1 embodiment of the present invention 1 and comparative example 1 obtain;
Fig. 2 is the XPS curve of the catalyst that the embodiment of the present invention 1 and comparative example 1 obtain;
Fig. 3 is the H of the modified electrode made of catalyst that embodiment and comparative example obtain in deoxygenation
2sO
4in cyclic voltammetry curve;
Fig. 4 is that the modified electrode made of catalyst prepared of the embodiment of the present invention 1 is at H
2sO
4cO in solution peels off curve and blank curve;
Fig. 5 is the H of modified electrode after deoxygenation that catalyst that the embodiment of the present invention and comparative example obtain is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH;
Fig. 6 is that the modified electrode made of catalyst that the embodiment of the present invention 2 obtains is at H
2sO
4cO in solution peels off curve and blank curve;
Fig. 7 is that the modified electrode made of catalyst that the embodiment of the present invention 3 obtains is at H
2sO
4cO in solution peels off curve and blank curve;
Fig. 8 is that the modified electrode made of catalyst that comparative example 2 of the present invention obtains is at H
2sO
4cO in solution peels off curve and blank curve;
Fig. 9 is that the modified electrode made of catalyst that comparative example 1 of the present invention obtains is at H
2sO
4cO in solution peels off curve and blank curve.
Detailed description of the invention
The invention provides a kind of preparation method of the catalyst for DMFC, comprise the following steps:
A) carbon substrate and potassium permanganate are carried out redox reaction in water, obtain carbon based catalyst support;
B) carbon based catalyst support described step a) obtained and the mixing of active material presoma, obtain the catalyst for DMFC after reaction.
The present invention first with carbon substrate and potassium permanganate for raw material, it is carried out redox reaction in aqueous phase, achieves the modification to carbon substrate, obtain carbon substrate catalyst carrier.
Carbon substrate is preferably first scattered in water by the present invention, obtains the suspension of carbon substrate; And then potassium permanganate is added in the suspension of described carbon substrate, obtain carbon based catalyst support after carrying out redox reaction, detailed process is as follows:
First carbon substrate is preferably scattered in water by the present invention, obtains the suspension of carbon substrate.Carbon substrate, preferably under ultrasonic condition, is scattered in water by the present invention, obtains the suspension of carbon substrate.The present invention, to described ultrasonic condition, as temperature, time etc. do not have special restriction, adopts ultrasonic technical scheme well known to those skilled in the art, until described carbon substrate be uniformly dispersed in water.In the present invention, described carbon substrate be preferably in active carbon, CNT and Graphene one or more, be more preferably active carbon, the source of the present invention to carbon substrate does not have special restriction, can adopt the commercial goods of carbon substrate, also can be self-control carbon substrate; The preparation method of the present invention to described self-control carbon substrate does not have special restriction, adopts the technology of preparing scheme of carbon substrate well known to those skilled in the art.Described water is preferably deionized water, is more preferably the deionized water that resistivity is not less than 18.2M Ω cm; The mass ratio of described carbon substrate and described water is preferably 80:(150 ~ 500), be more preferably 80:(180 ~ 300); The described ultrasonic time is preferably 1h ~ 5h, is more preferably 1.5h ~ 3h.
After obtaining the suspension of carbon substrate, the present invention adds potassium permanganate in the suspension of described carbon substrate, after carrying out redox reaction, obtains carbon based catalyst support.The present invention is preferably under the condition stirred, potassium permanganate is added in the suspension of described carbon substrate, the method of the present invention to described stirring does not have special restriction, adopt the technical scheme of stirring well known to those skilled in the art, in the present invention, described stirring can be artificial stirring, and can be also mechanical agitation, described stirring be preferably magnetic agitation; The mass ratio of described potassium permanganate and the carbon substrate described in technique scheme is preferably (0.5 ~ 8): 80, is more preferably (1.2 ~ 5.4): 8; The time of described redox reaction is preferably 1 hour ~ 10 hours, is more preferably 4 hours ~ 8 hours.
The present invention with carbon substrate and potassium permanganate for raw material, it is carried out one pot reaction in aqueous phase, can carbon based catalyst support be obtained, simple to the preparation process of carbon based catalyst support in preparation method provided by the invention, be easy to operation, be beneficial to the extensive synthesis of carbon based catalyst support.
After obtaining carbon based catalyst support, the present invention is by described carbon based catalyst support and the mixing of active material presoma, obtain the catalyst for DMFC after reaction, described catalyst comprises carbon based catalyst support and is carried on the active material on described carrier.In the process, described active material is deposited on described carbon based catalyst support, achieve the load to active material, the method for the present invention to described deposition does not have special restriction, adopts the technical scheme that active material well known to those skilled in the art deposits on a catalyst support.In the present invention, described active material presoma is preferably precious metal ion, is more preferably one or more in platinum ion, gold ion, ruthenium ion or silver ion, is more preferably platinum ion; The mass ratio of described carbon based catalyst support and described active material presoma is preferably 1:(1 ~ 10), be more preferably 1:(3 ~ 8).In the present invention, when described active material presoma is precious metal ion, described by described carbon based catalyst support and the mixing of active material presoma, the catalyst obtained after reaction for DMFC preferably specifically comprises the following steps:
B1) carbon based catalyst support described step a) obtained and the mixing of active material precursor solution, obtain mixed solution;
B2) described step b1) add reducing agent in the mixed solution that obtains, obtain the catalyst for DMFC after reaction.
The present invention preferably first prepares the solution of active material presoma, is then mixed with institute carbon based catalyst support by described active material precursor solution, obtains mixed solution.The compound method of the present invention to described active material precursor solution does not have special restriction, the technical scheme of the active material precursor solution preparation adopting those skilled in the art to know.After obtaining active material precursor solution, the present invention carries out the post processing of load without the need to the carbon based catalyst support obtained technique scheme, preferably directly described active material precursor solution to be joined in the carbon based catalyst support that technique scheme obtains, obtain mixed solution.In the present invention, the mass concentration of described active material precursor solution is preferably (10 ~ 30) mg
expensive metal/ mL, is more preferably (15 ~ 25) mg
noble metal/ mL.When described active material presoma is platinum ion, described active material precursor solution is preferably platinum acid chloride solution; When described active material presoma is gold ion, described active material precursor solution is preferably chlorauric acid solution; When described active material presoma is silver ion, described active material precursor solution is preferably silver nitrate.After described active material precursor solution is mixed with described carbon based catalyst support, the present invention preferably stirs it, obtain mixed solution, the method for the present invention to described stirring is not particularly limited, and adopts the technical scheme of stirring well known to those skilled in the art.In the present invention, can adopt the artificial mode stirred, also can adopt churned mechanically mode, the time of described stirring is preferably 1 hour ~ 10 hours, is more preferably 3 hours ~ 6 hours.
After obtaining mixed solution, the present invention adds reducing agent in described mixed solution, and the active material simple substance formed after reaction is deposited on described carbon based catalyst support, obtains the catalyst for DMFC.The present invention preferably dropwise adds reducing agent under the condition stirred in described mixed solution, and described reducing agent is preferably NaBH
4, be more preferably NaBH
4solution, described NaBH
4the mass concentration of solution is preferably 0.1mg/mL ~ 5mg/mL, is more preferably 1mg/mL ~ 3mg/mL.The present invention preferably carries out described reaction under the condition stirred, in course of reaction, the active material presoma in described mixed solution is reduced agent reduction, obtains active material simple substance, thus described active material is deposited on described carbon based catalyst support, obtain catalyst.Described catalyst comprises carbon based catalyst support and is carried on the active material on described carrier.The mass ratio of described reducing agent and active material is preferably 2:(1 ~ 8), be more preferably 2:(3 ~ 5); The time of described reaction is preferably 4h ~ 15h, is more preferably 6h ~ 10h.
After having reacted, the reactant liquor obtained preferably is carried out suction filtration and washing by the present invention, and the method for the present invention to described suction filtration and washing does not have special restriction, adopts the technical scheme of suction filtration well known to those skilled in the art and washing.In the present invention, described washing preferably spends deionized water, and described deionized water is preferably the deionized water that resistivity is not less than 18.2M Ω cm, until without Cl in filtrate
-exist; Then the solid obtained preferably is carried out vacuum drying at 60 DEG C ~ 80 DEG C, be more preferably 65 DEG C ~ 75 DEG C, obtain the catalyst for methanol fuel cell.The present invention is to Cl in detection filtrate
-method there is no special restriction, adopt detection Cl well known to those skilled in the art
-method.In the present invention, liquor argenti nitratis ophthalmicus can be added in described filtrate, if occurred without precipitation, then illustrate in filtrate without Cl
-, now washed.
The present invention carries out X-ray diffraction test after being ground by the catalyst being used for DMFC obtained, scanning angle is 10 ° ~ 90 °, sweep speed is 5 °/min, obtain the XRD collection of illustrative plates of supported hybrid catalyst, experimental result shows, the carbon based catalyst support being doped with Mn does not affect for the accumulation mode of load pt atom in the platinum of carrier surface; The present invention carries out X-ray electron spectroscopy analysis after being ground by the supported hybrid catalyst obtained, and obtain its XPS collection of illustrative plates, experimental result shows, the introducing of Mn element does not cause obvious electronic effect.
The present invention is used for what obtain the catalysis that DMFC catalyst is used for methyl alcohol, and test its chemical property, detailed process is as follows:
The present invention is using the supported hybrid catalyst that obtains as the decorative material of electrode, and obtain modified electrode, using modified electrode as working electrode, the three-electrode system obtained as to electrode, is placed in the H of nitrogen deoxygenation as reference electrode, Pt sheet by Ag/AgCl electrode
2sO
4in solution, carry out cyclic voltammetry scan analysis, obtain modified electrode at H
2sO
4cyclic voltammetry curve in solution, obtains the electrochemical surface area of supported hybrid catalyst provided by the invention by integral and calculating according to the cyclic voltammetry curve obtained.Experimental result shows, the electrochemical surface area of supported hybrid catalyst provided by the invention is up to 102.90m
2/ g.
Preferably carry out in accordance with the following methods in the preparation of modified electrode of the present invention:
Catalyst for DMFC provided by the invention is scattered in Nafion solution, obtains the dispersion liquid of catalyst;
Described dispersant liquid drop is applied on glass-carbon electrode, after drying, obtains modified electrode.
The described catalyst being used for DMFC, preferably under ultrasonic condition, is scattered in Nafion solution, obtains the dispersion liquid of catalyst by the present invention.In the present invention, in the catalyst dispersion obtained, the mass concentration of catalyst is preferably 1mg/ μ L ~ 8mg/ μ L, and the described ultrasonic time is preferably 20min ~ 50min;
After obtaining dispersion liquid, described dispersant liquid drop is applied on glass-carbon electrode by the present invention, obtains modified electrode after drying.Described dripping is applied to the volume of dispersion liquid on glass-carbon electrode and is preferably 3 μ L ~ 15 μ L in the present invention, is more preferably 5 μ L ~ 10 μ L; The present invention does not have special restriction to the parameter of described glass-carbon electrode such as diameter etc., adopts glass-carbon electrode well known to those skilled in the art; Drip after painting completes, the present invention has the glass-carbon electrode of dispersion liquid preferably at room temperature to dry by dripping, and obtain modified electrode, the present invention does not have special restriction to described method of drying, and can dry under field conditions (factors), can dry under infrared lamp yet.
After obtaining modified electrode, the present invention with described modified electrode for working electrode, using Ag/AgCl electrode as reference electrode, Pt sheet as to electrode, obtain three-electrode system.The molar concentration that described three-electrode system is preferably placed in nitrogen deoxygenation by the present invention is the H of 0.5mol/L
2sO
4in solution, carry out cyclic voltammetry scan test, the method of the present invention to described cyclic voltammetry scan does not have special restriction, adopt the technical scheme of cyclic voltammetry scan well known to those skilled in the art, in the present invention, the speed of sweeping of described cyclic voltammetry scan is preferably 10mV/s ~ 100mV/s, is more preferably 20mV/s ~ 80mV/s.
The present invention have detected the catalyst for DMFC that obtains to the anti-poisoning ability of intermediate oxidation product CO, and the present invention is with the H described in technique scheme
2sO
4solution is test end liquid, at described H
2sO
4carry out the experiment of CO adsorption desorption in solution, the method for the present invention to described CO adsorption desorption does not have special restriction, adopts the technical scheme of CO adsorption desorption well known to those skilled in the art.The present invention chooses double-deck district current potential to described H
2sO
4in solution after logical CO gas 15min, use high-purity N
2cO in removing solution, carries out cyclic voltammetry scan in the solution then after removing CO, obtains the H after CO adsorption desorption
2sO
4the cyclic voltammogram of solution on modified electrode, experimental result shows, catalyst provided by the invention is adsorbed with obvious inhibitory action to CO, and the oxidation peak current potential of CO is negative moves, more be conducive to the oxidation of CO, this illustrates, catalyst provided by the invention has the ability of higher anti-CO toxicity.
The catalyst being used for DMFC obtained is used for the catalysis to methyl alcohol by the present invention, and detailed process is as follows:
Three-electrode system technique scheme obtained is placed in the H containing methyl alcohol
2sO
4in solution, carry out cyclic voltammetry scan, obtain the cyclic voltammetry curve on modified electrode that methyl alcohol makes at catalyst.
The present invention is in order to test the catalytic performance of described catalyst to methyl alcohol, and three-electrode system technique scheme obtained is placed in the H containing methyl alcohol
2sO
4in solution, carry out cyclic voltammetry scan, obtain the cyclic voltammetry curve on modified electrode that methyl alcohol makes at catalyst, the catalytic performance of described catalyst to methyl alcohol can be drawn according to the cyclic voltammetry curve obtained.In the present invention, the described H containing methyl alcohol
2sO
4in solution, the molar concentration of methyl alcohol is preferably 0.1mol/L ~ 1.0mol/L, is more preferably 0.5mol/L, H
2sO
4the molar concentration of solution is preferably 0.5mol/L; The present invention, to the parameter of described cyclic voltammetry scan, as sweep speed etc. does not have special restriction, adopts the technical scheme of cyclic voltammetry scan well known to those skilled in the art.Experimental result shows, on the modified electrode that catalyst provided by the invention is made, the oxidation peak current potential of methyl alcohol is negative to be moved, and this explanation is easier to the oxidation of methyl alcohol; The oxidation peak current of methyl alcohol increases, and this illustrates, the oxidation of catalyst to methyl alcohol for DMFC provided by the invention has good catalytic performance.
The invention provides a kind of DMFC, comprise Methanol Anode, oxygen cathode, catalyst and PEM, it is characterized in that, the catalyst for DMFC that described catalyst obtains for preparation method described in technique scheme.The present invention does not have special restriction to other parts except catalyst of described DMFC and annexation thereof, adopt the structure of DMFC well known to those skilled in the art, as long as the catalyst for DMFC that catalyst wherein used adopts preparation method provided by the invention to obtain.
The invention provides a kind of preparation method of the catalyst for DMFC, comprise the following steps: a) carbon substrate and potassium permanganate are carried out redox reaction in water, obtain carbon based catalyst support; B) carbon based catalyst support described step a) obtained and the mixing of active material presoma, obtain the catalyst for DMFC after reaction.Preparation method provided by the invention is with carbon substrate and potassium permanganate for raw material, and it being carried out in aqueous phase one pot reaction can obtain carbon based catalyst support.Then without the need to carrying out complicated post processing to described carbon based catalyst support, directly on the carbon based catalyst support obtained, depositing described active material, is the available catalyst for DMFC after reaction; And in method provided by the invention, described carbon substrate and described potassium permanganate carry out one pot reaction in aqueous phase, can obtain carbon based catalyst support.Method provided by the invention is without the need to carrying out the post processing of load to the carbon based catalyst support obtained, method is simple, is easy to operation, is beneficial to large-scale industrial production.Preparation method provided by the invention obtains catalyst and has higher methyl alcohol electro catalytic activity and CO tolerance catalysts ability, and the performance for DMFC provides a kind of support preparation method of simple and easy green.Experimental result shows, the electrochemical active surface of the catalyst that method provided by the invention obtains is up to 102.90m
2/ g, its oxidation peak current potential CO being oxidized to the CO obtained is born and is moved, and namely CO can be oxidized away by easier on catalyst provided by the invention, thus can not affect the catalysis of catalyst to methanol oxidation; It is when the oxidation of catalysis methanol, and the oxidation peak current potential of methyl alcohol is negative to be moved, and the electric current of oxidation peak is up to 682.73A/g.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of preparation method of carbon based catalyst support provided by the invention and the preparation method of supported hybrid catalyst being described in detail, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
By model be the conductive black 80mg of Vulcan XC-72R by ultrasonic disperse in 200mL deionized water, obtain the dispersion liquid of conductive black, described deionization resistivity of water is 18.2M Ω cm, adds 1.4mg KMnO under magnetic stirring in described conductive black
4, react 6h under stirring, obtain carbon based catalyst support.
After above-mentioned reaction completes, in the reactant liquor obtained, add 1.105mL mass concentration is 18.105mgPt/mL chloroplatinic acid aqueous solution, and at room temperature stir after 4 hours, dropwise dripping mass concentration is wherein the NaBH of 1mg/mL
4solution, after continuing to stir 5h, the reactant liquor obtained is carried out suction filtration, and spend deionized water, described deionization resistivity of water is 18.2M Ω cm, and suction filtration is extremely without Cl
-exist, finally by solid vacuum drying at 80 DEG C, obtain the carbon based catalyst support of Supported Pt Nanoparticles, namely for the catalyst of DMFC.
The present invention carries out X-ray diffraction scanning analysis after being ground by the catalyst obtained, scanning angle is 10 ° ~ 90 °, sweeping speed is 5 °/min, result as shown in Figure 1, Fig. 1 is the XRD curve of the catalyst that the embodiment of the present invention 1 and comparative example 1 obtain, wherein, wherein curve 1 is the XRD curve of the catalyst that the embodiment of the present invention 1 obtains, curve 2 is the XRD curve of the catalyst that comparative example 1 obtains, can be found out by the curve 1 in comparison diagram 2 and curve 2, in catalyst carrier provided by the invention, the doping of Mn does not affect for the accumulation mode of load Pt atom in the Pt nano particle of carrier surface, that is, the carbon based catalyst support 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 being ground by the catalyst obtained, result as shown in Figure 2, Fig. 2 is the XPS curve of the catalyst that the embodiment of the present invention 1 and comparative example 1 obtain, wherein curve 1 is the XPS curve of the catalyst that embodiment 1 obtains, curve 2 is the XPS curve of the catalyst that comparative example 1 obtains, can be found out by the curve 1 in comparison diagram 2 and curve 2, the introducing of the Mn element in carbon based catalyst support provided by the invention does not cause obvious electronic effect, that is, carbon based catalyst support provided by the invention is in carrying active substance, the impact that the introducing of Mn element can not cause the electronic effect of catalyst, thus also would not impact its catalytic performance.
The catalyst that 5mg the present embodiment obtains is joined ultrasonic disperse 30min in 50 μ L Nafion solution, obtain the dispersion soln of catalyst; Being dripped by the dispersion soln of catalyst described in 10 μ L is applied on glass-carbon electrode, at room temperature dries, obtains modified electrode.
With described modified electrode for working electrode, Ag/AgCl electrode, as reference electrode, using Pt sheet as to electrode, utilizes three-electrode system, 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, as shown in Figure 3, Fig. 3 is the H of the modified electrode made of catalyst that embodiment and comparative example obtain in deoxygenation to result
2sO
4in cyclic voltammetry curve, wherein curve 1 is the H of the modified electrode made of catalyst that embodiment 1 obtains in deoxygenation
2sO
4in cyclic voltammetry curve, by the curve 1 in Fig. 3 by calculating the electrochemical surface area of catalyst obtaining the present embodiment and prepare, result is as shown in table 1, and table 1 is the performance test results of the catalyst that the embodiment of the present invention and comparative example obtain.
The present invention is tested by CO adsorption desorption, investigates the electrochemical surface area of catalyst provided by the invention and the ability of its anti-CO toxicity.The present invention is at above-mentioned H
2sO
4in solution, carry out the experiment of CO adsorption desorption, choose after double-deck district current potential leads to CO gas 15min and use high-purity N
2cO in removing solution, and then carries out cyclic voltammetry scan, and the scanning number of turns is 2 circles, and as shown in Figure 4, Fig. 4 is that the modified electrode made of the embodiment of the present invention 1 Kaolinite Preparation of Catalyst is at H to result
2sO
4cO in solution peels off curve and blank curve, and can be drawn the CO adsorption desorption active surface area of catalyst by Fig. 4, result is as shown in table 1, and table 1 is the characterization result of the catalyst performance that the embodiment of the present invention and comparative example obtain.And can be found out by comparison diagram 9, on the modified electrode that the catalyst prepared at the present embodiment is made, the oxidation peak current potential of CO is negative to be moved, and this illustrates on the electrode that CO modifies at catalyst provided by the invention more easily oxidized, thus reduces 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 nitrogen deoxygenation is the H of 0.5mol/L
2sO
4be the CH of 0.5mol/L with molar concentration
3carry out cyclic voltammetry scan in the mixed solution of OH, as shown in Figure 5, Fig. 5 is the H of modified electrode after deoxygenation that catalyst that the embodiment of the present invention and comparative example obtain is made to result
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, wherein curve 1 is the H of modified electrode after deoxygenation that catalyst that embodiment 1 obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, curve 4 is the H of modified electrode after deoxygenation that catalyst that comparative example 1 of the present invention obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, can be found out by the curve 1 in comparison diagram 5 and curve 4, the modified electrode that catalyst provided by the invention obtains is when catalysis methanol, the oxidizing potential of methyl alcohol reduces, oxidation current is improved, this illustrates, catalyst provided by the invention has the performance of higher catalysis methanol.
Embodiment 2
The conductive black being Vulcan XC-72R with 80mg model and 2.7mg KMnO
4for raw material, obtain carbon based catalyst support according to the method described in embodiment 1, according to the deposited catalyst platinum on described carbon based catalyst support of the method described in embodiment 1, obtain the catalyst for DMFC.The 5mg catalyst obtained is joined ultrasonic disperse 30min in 50 μ L Nafion solution, 1mL ethanol, obtain the dispersion soln of catalyst; Being dripped by the dispersion soln of catalyst described in 10 μ L is applied on glass-carbon electrode, at room temperature dries, obtains modified electrode.
With described modified electrode for working electrode, Ag/AgCl electrode, as reference electrode, using Pt sheet as to electrode, utilizes three-electrode system, 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, as shown in Figure 3, Fig. 3 is the H of the modified electrode made of catalyst that embodiment and comparative example obtain in deoxygenation to result
2sO
4in cyclic voltammetry curve.Wherein curve 2 is the H of the modified electrode made of catalyst that embodiment 2 obtains in deoxygenation
2sO
4in cyclic voltammetry curve, by the curve 2 in Fig. 3 by calculating the electrochemical surface area of catalyst obtaining the present embodiment and prepare, result is as shown in table 1, and table 1 is the performance test results of the catalyst that the embodiment of the present invention and comparative example obtain.
The present invention, according to the CO De contamination process described in embodiment 1, has investigated the electroactive area of catalyst prepared by the present embodiment and the ability of its anti-CO toxicity, and as shown in Figure 6, Fig. 6 is that the modified electrode made of catalyst prepared by the embodiment of the present invention 2 is at H to result
2sO
4cO in solution peels off curve and curve, and wherein curve 1 be that the modified electrode made of the catalyst of the embodiment of the present invention 2 preparation is at H
2sO
4cO in solution peels off curve, and curve 2 be that the modified electrode made of the catalyst of the embodiment of the present invention 2 preparation is at H
2sO
4the blank curve of CO in solution, can draw CO adsorption desorption active surface area by Fig. 4, result is as shown in table 1, and table 1 is the characterization result of the catalyst performance that the embodiment of the present invention and comparative example obtain.And can be found out by comparison diagram 9, on the modified electrode that the catalyst prepared at the present embodiment is made, the oxidation peak current potential of CO is negative to be moved, and this illustrates on the electrode that CO modifies at catalyst provided by the invention more easily oxidized, thus reduces its poisoning effect.
The present invention, according to the process described in embodiment 1, has investigated catalyst prepared by the present embodiment to the catalytic capability of methyl alcohol, and as figure 5 illustrates, Fig. 5 is the H of modified electrode after deoxygenation that catalyst that the embodiment of the present invention and comparative example obtain is made to result
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, wherein curve 2 is the H of modified electrode after deoxygenation that catalyst that embodiment 2 obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, curve 4 is the H of modified electrode after deoxygenation that catalyst that comparative example 1 of the present invention obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, can be found out by the curve 2 in comparison diagram 5 and curve 4, the modified electrode that catalyst provided by the invention obtains is when catalysis methanol, the oxidizing potential of methyl alcohol reduces, oxidation current is improved, and this illustrates, catalyst provided by the invention has the performance of higher catalysis methanol.
Embodiment 3
The conductive black being Vulcan XC-72R with 80mg model and 5.4mg KMnO
4for raw material, obtain carbon based catalyst support according to the method described in embodiment 1, according to the deposited catalyst platinum on described carbon based catalyst support of the method described in embodiment 1, obtain the catalyst for DMFC.The 5mg catalyst obtained is joined ultrasonic disperse 30min in 50 μ L Nafion solution, 1mL ethanol, obtain the dispersion soln of catalyst; Being dripped by the dispersion soln of catalyst described in 10 μ L is applied on glass-carbon electrode, at room temperature dries, obtains modified electrode.
With described modified electrode for working electrode, Ag/AgCl electrode, as reference electrode, using Pt sheet as to electrode, utilizes three-electrode system, 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, as shown in Figure 3, Fig. 3 is the H of the modified electrode made of catalyst that embodiment and comparative example obtain in deoxygenation to result
2sO
4in cyclic voltammetry curve.Wherein curve 2 is the H of the modified electrode made of catalyst that embodiment 2 obtains in deoxygenation
2sO
4in cyclic voltammetry curve, by the curve 2 in Fig. 3 by calculating the electrochemical surface area of catalyst obtaining the present embodiment and prepare, result is as shown in table 1, and table 1 is the performance test results of the catalyst that the embodiment of the present invention and comparative example obtain.
The present invention, according to the CO adsorption desorption process described in embodiment 1, has investigated the electroactive area of catalyst prepared by the present embodiment and the ability of its anti-CO toxicity, and as shown in Figure 7, Fig. 7 is that the modified electrode made of catalyst prepared by the embodiment of the present invention 3 is at H to result
2sO
4cO in solution peels off curve and blank curve, and wherein curve 1 be that the modified electrode made of the catalyst of the embodiment of the present invention 3 preparation is at H
2sO
4cO in solution peels off curve, and curve 2 be that the modified electrode made of the catalyst of the embodiment of the present invention 3 preparation is at H
2sO
4the blank curve of CO in solution, can draw CO adsorption desorption active surface area by Fig. 7, result is as shown in table 1, and table 1 is the characterization result of the catalyst performance that the embodiment of the present invention and comparative example obtain.And can be found out by comparison diagram 9, on the modified electrode that the catalyst prepared at the present embodiment is made, the oxidation peak current potential of CO is negative to be moved, and this illustrates on the electrode that CO modifies at catalyst provided by the invention more easily oxidized, thus reduces its poisoning effect.
The present invention, according to the process described in embodiment 1, has investigated catalyst prepared by the present embodiment to the catalytic capability of methyl alcohol, and as shown in Figure 5, Fig. 5 is the H of modified electrode after deoxygenation that catalyst that the embodiment of the present invention and comparative example obtain is made to result
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, wherein curve 3 is the H of modified electrode after deoxygenation that catalyst that embodiment 3 obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, curve 4 is the H of modified electrode after deoxygenation that catalyst that comparative example 1 of the present invention obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, can be found out by the curve 3 in comparison diagram 5 and curve 4, the modified electrode that catalyst provided by the invention obtains is when catalysis methanol, the oxidizing potential of methyl alcohol reduces, oxidation current is improved, this illustrates, catalyst provided by the invention has the performance of higher catalysis methanol.
Embodiment 4
The supported hybrid catalyst obtained using embodiment 1, as the catalyst in DMFC, by itself and methyl alcohol, oxygen and PEM compound, is conventionally prepared the method for DMFC, is prepared DMFC.
The present invention has investigated the performance of the DMFC obtained, and result shows, adopt the catalyst that preparation method of the present invention obtains, it has good catalytic performance to methyl alcohol, and has the ability of higher resisting CO poison.
Comparative example 1
With model be the conductive black 80mg of Vulcan XC-72R as catalyst carrier, adopt the method for embodiment 1, prepare catalyst.
The present invention carries out X-ray diffraction scanning analysis after being ground by the catalyst obtained, scanning angle is 10 ° ~ 90 °, sweeping speed is 5 °/min, result as shown in Figure 1, Fig. 1 is the XRD curve of the catalyst that the embodiment of the present invention 1 and comparative example 1 obtain, wherein, curve 2 is the XRD curve of the catalyst that comparative example 1 obtains, can be found out by the curve 1 in comparison diagram 2 and curve 2, Mn in catalyst carrier provided by the invention does not affect for the accumulation mode of the Pt atom of load in the Pt nano particle of carrier surface, that is, carbon based catalyst support provided by the invention 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 being ground by the catalyst obtained, result as shown in Figure 2, Fig. 2 is the XPS curve of the catalyst that the embodiment of the present invention 1 and comparative example 1 obtain, wherein curve 2 is the XPS curve of the catalyst that comparative example 1 obtains, can be found out by the curve 1 in comparison diagram 2 and curve 2, the introducing of the Mn element in carbon based catalyst support provided by the invention does not cause obvious electronic effect, that is, carbon based catalyst support provided by the invention is in carrying active substance, the introducing of Mn element can not impact the electronic effect of catalyst, thus also would not impact its catalytic performance.
The 5mg catalyst obtained is joined ultrasonic disperse 30min in 50 μ L Nafion solution, 1mL ethanol, obtain the dispersion soln of catalyst; Being dripped by the dispersion soln of catalyst described in 10 μ L is applied on glass-carbon electrode, at room temperature dries, obtains modified electrode.
With described modified electrode for working electrode, Ag/AgCl electrode, as reference electrode, using Pt sheet as to electrode, utilizes three-electrode system, 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, as shown in Figure 3, Fig. 3 is the H of the modified electrode made of catalyst that embodiment and comparative example obtain in deoxygenation to result
2sO
4in cyclic voltammetry curve, wherein curve 5 is the H of the modified electrode made of catalyst that comparative example 1 obtains in deoxygenation
2sO
4in cyclic voltammetry curve, by the curve 5 in Fig. 3 by calculating the electrochemical surface area of catalyst obtaining this comparative example and prepare, result is as shown in table 1, and table 1 is the performance test results of the catalyst that the embodiment of the present invention and comparative example obtain.
The present invention is according to the CO De contamination process described in embodiment 1, the electrochemical surface area of the catalyst that comparative example of the present invention provides and the ability of its anti-CO toxicity are investigated, as shown in Figure 9, Fig. 9 is that the modified electrode made of catalyst of comparative example 1 of the present invention preparation is at H to result
2sO
4cO in solution peels off curve and blank curve, and wherein curve 1 be that the modified electrode made of catalyst prepared by comparative example 1 of the present invention is at H
2sO
4cO in solution peels off curve, and the modified electrode that the catalyst that curve 2 is prepared for comparative example of the present invention is made is at H
2sO
4the blank curve of CO in solution, can obtain CO adsorption desorption active surface area by Fig. 9, result is as shown in table 1, and table 1 is the characterization result of the catalyst performance that the embodiment of the present invention and comparative example obtain.And by with the curve comparison in Fig. 4, Fig. 6, Fig. 7, on the modified electrode that the catalyst prepared in the embodiment of the present invention is made, the oxidation peak current potential of CO is negative to be moved, and this illustrates on the electrode that CO modifies at catalyst provided by the invention more easily oxidized, thus reduces its poisoning effect.
The present invention, according to the process described in embodiment 1, has investigated catalyst prepared by this comparative example to the catalytic capability of methyl alcohol, and as shown in Figure 5, Fig. 5 is the H of modified electrode after deoxygenation that catalyst that the embodiment of the present invention and comparative example obtain is made to result
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, wherein curve 5 is the H of modified electrode after deoxygenation that catalyst that comparative example 1 obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, by the curve 5 in Fig. 5 is compared with curve 1, curve 2 can find out with curve 3, the modified electrode that catalyst provided by the invention obtains is when catalysis methanol, the oxidizing potential of methyl alcohol reduces, oxidation current is improved, this illustrates, catalyst provided by the invention has the performance of higher catalysis methanol.
Comparative example 2
The conductive black being Vulcan XC-72R with 80mg model and 8.1mg KMnO
4for raw material, obtain carbon based catalyst support according to the method described in embodiment 1, according to the deposited catalyst platinum on described carbon based catalyst support of the method described in embodiment 1, obtain the catalyst for DMFC.The 5mg catalyst obtained is joined ultrasonic disperse 30min in 50 μ L Nafion solution, obtain the dispersion soln of catalyst; Being dripped by the dispersion soln of catalyst described in 10 μ L is applied on glass-carbon electrode, at room temperature dries, obtains modified electrode.
The present invention, according to the CO De contamination process described in embodiment 1, has investigated the electroactive area of catalyst prepared by this comparative example and the ability of its anti-CO toxicity, and as shown in Figure 8, Fig. 8 is that the modified electrode made of the catalyst of comparative example 2 of the present invention preparation is at H to result
2sO
4cO in solution peels off curve and blank curve, and wherein curve 1 be that the modified electrode made of catalyst prepared by comparative example 2 of the present invention is at H
2sO
4cO in solution peels off curve, and curve 2 be that the modified electrode made of catalyst prepared by comparative example 2 of the present invention is at H
2sO
4the blank curve of CO in solution, can obtain CO adsorption desorption active surface area by Fig. 8, result is as shown in table 1, and table 1 is the characterization result of the catalyst performance that the embodiment of the present invention and comparative example obtain.And by the curve in comparison diagram 9, on the modified electrode that comparative example Kaolinite Preparation of Catalyst of the present invention is made, the oxidation peak current potential of CO is negative to be moved, this illustrates on the electrode that CO modifies at catalyst provided by the invention more easily oxidized, thus reduces its poisoning effect.
The present invention, according to the process described in embodiment 1, has investigated catalyst prepared by the present embodiment to the catalytic capability of methyl alcohol, and as figure 5 illustrates, Fig. 5 is the H of modified electrode after deoxygenation that catalyst that the embodiment of the present invention and comparative example obtain is made to result
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, wherein curve 5 is the H of modified electrode after deoxygenation that catalyst that comparative example 2 obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, curve 4 is the H of modified electrode after deoxygenation that catalyst that comparative example 1 of the present invention obtains is made
2sO
4and CH
3cyclic voltammetry curve in the mixed solution of OH, can be found out by the curve 4 in comparison diagram 5 and curve 5, the modified electrode that the catalyst that comparative example 2 of the present invention provides obtains is when catalysis methanol, the oxidation current of methyl alcohol is reduced, this explanation, in catalyst carrier provided by the invention, the doping of too high Mn can cause the ability of the catalyst methanol oxidation obtained to reduce.
The experimental result that table 1 embodiment of the present invention and comparative example obtain
As can be seen from Table 1, hydrogen adsorption desorption active surface area, CO adsorption desorption active surface area present the trend of first increases and then decreases with the raising of Mn doping, but the sample of doped with Mn is relative to being adsorbed with inhibitory action significantly for CO in comparative example 1.And contrasting the oxidation peak current potential of CO, the sample that embodiment and comparative example 2 obtain all comparatively has negative in various degree moving to comparative example 1, proves that Mn is doped with being beneficial to the oxidation poisoning middle species.And mixing of Mn makes that the oxidation peak current potential of methyl alcohol is negative to be moved, methanol oxidation namely can be made to be more prone to, and along with the increase of doping, peak point current also present the trend of first increases and then decreases, namely in doping, there is an optimal value, the 5.4mg KMnO namely in embodiment 3
2/ 80mgVulcan72R.
As seen from the above embodiment, the invention provides a kind of preparation method of the supported hybrid catalyst for DMFC, carbon substrate and potassium permanganate are carried out redox reaction in water, obtains carbon based catalyst support; Then position activity material on the carbon based catalyst support obtained, the catalyst for DMFC obtained after reaction.The present invention has obtained carbon based catalyst support by one pot reaction, and to the carbon based catalyst support obtained without the need to carrying out complicated post processing, after the carbon based catalyst support obtained, directly carry out the deposition of active material thereon, the catalyst for DMFC after reaction, can be obtained.Method provided by the invention is simple, be easy to operation, and the catalyst carrier obtained has good performance.In preparation method provided by the invention, pass through redox reaction, mixing of Mn is had in the carbon based catalyst support obtained, be 80:(0.5 ~ 8 at the mass ratio of carbon substrate and described potassium permanganate) between, along with the quality of potassium permanganate raises, the content of the Mn mixed also just increases, to the mithridatism ability of CO be obtained for larger raising to the catalytic capability of methanol oxidation after making its supported catalyst.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1., for a preparation method for the catalyst of DMFC, comprise the following steps:
A) carbon substrate and potassium permanganate are carried out redox reaction in water, obtain carbon based catalyst support;
B1) carbon based catalyst support described step a) obtained and the mixing of active material precursor solution, obtain mixed solution;
B2) described step b1) add reducing agent in the mixed solution that obtains, obtain the catalyst for DMFC after reaction;
The time of described redox reaction is 1h ~ 10h;
Described active material presoma is precious metal ion.
2. the preparation method of the catalyst for DMFC according to claim 1, is characterized in that, described carbon substrate is one or more in active carbon, CNT and Graphene.
3. the preparation method of the catalyst for DMFC according to claim 1, is characterized in that, the mass ratio of carbon substrate and described potassium permanganate is 80:(0.5 ~ 8).
4. the preparation method of the catalyst for DMFC according to claim 1, is characterized in that, described water is the deionized water that resistivity is not less than 18.2M Ω cm.
5. the preparation method of the catalyst for DMFC according to claim 1, is characterized in that, described active material presoma is one or more in platinum ion, gold ion, ruthenium ion or silver ion.
6. the preparation method of the catalyst for DMFC according to claim 1, is characterized in that, the mass ratio of described carbon based catalyst support and described active material presoma is 1:(1 ~ 10).
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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 |