CN102658201B - Preparation method of direct methanol fuel cell anode composite membrane catalyst - Google Patents
Preparation method of direct methanol fuel cell anode composite membrane catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000012528 membrane Substances 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title abstract description 51
- 239000000446 fuel Substances 0.000 title abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 33
- 238000004070 electrodeposition Methods 0.000 claims abstract description 20
- 238000001338 self-assembly Methods 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 45
- 229910021389 graphene Inorganic materials 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 29
- 238000012986 modification Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 229920003169 water-soluble polymer Polymers 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000013460 polyoxometalate Substances 0.000 abstract 4
- 229910021397 glassy carbon Inorganic materials 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 239000010410 layer Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000000707 layer-by-layer assembly Methods 0.000 description 2
- 238000001907 polarising light microscopy Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910016525 CuMo Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 mineral carbon alkene Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a preparation method of a direct methanol fuel cell anode composite membrane catalyst, which comprises the following steps: previously preparing functional modified graphene, and pretreating a glassy carbon electrode substrate; carrying out layer-by-layer selfassembly on the functional modified graphene and polyoxometalate on the electrode to obtain a composite membrane of which the outermost layer is the functional modified graphene and polyoxometalate; and carrying out in-situ electrodeposition to obtain the anode composite membrane catalyst composed of the Pt nanoparticles, functional modified graphene and polyoxometalate. The composite membrane catalyst provided by the invention is prepared for the first time, and can be used as a direct methanol fuel cell anode catalyst. Compared with the pure platinum catalyst, the introduction of the functional modified graphene and polyoxometalate obviously enhances the electrocatalytic activity and CO poisoning resistance of the composite membrane catalyst; and the preparation method is simple, and has the advantage of lower cost. The invention provides a novel direct methanol fuel cell anode catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of DMFC anodic composite film catalyst, relate in particular to a kind of preparation method for the self assembly film catalyst anode-catalyzed reaction of DMFC and that formed by nano platinum particle, functional modification Graphene and polyoxometallate.
Background technology
The advantages such as DMFC (DMFC) is extensive with its fuel source, convenient storage, simple in structure, reliability is strong, pollution-free, the continued power time is long are paid close attention to day by day widely, and are with a wide range of applications.But, the intermediate product of methanol oxidation process can be by strong adsorption at catalyst surface, make catalyst poisoning, reduced activity, along with poisoning the accumulation of intermediate product at electrode surface, methanol oxidation electric current constantly declines, and for these problems, finding new catalyst efficient, antitoxinization is the key that improves DMFC power density and promote its application.
Polyoxometallate (POMs) has nano-scale, unique topological structure, multifunction electronic and redox property, and it will be shown to good electrocatalysis characteristic for modified electrode.Layer-by-layer self-assembly (Layer-by-Layer Self-Assembly, LBL) technology, preparation process is simple, do not need complicated instrument and equipment, film forming is not subject to the restriction of substrate sizes and shape, the film of preparation has the plurality of advantages such as good machinery and chemical stability, is widely used in constructing orderly polyoxometallate organic and inorganic composite membrane.
Graphene (GN) is the monolayer of graphite, has two-dimension plane structure, can build zero dimension fullerene, one dimension CNT and three-dimensional graphite, and the basic and applied research of relevant Graphene also becomes one of hot subject of material science Disciplinary Frontiers.In methanol fuel cell field, Graphene and compound thereof are widely used because having good electrocatalysis characteristic.Document (S.Guo, S.Dong, E.Wang, ACS Nano 4 (2009) 547; Z.Wen, S.Yang, Y.Liang, W.He, H.Tong, L.Hao, X.Zhang, Q.Song, Electrochim.Acta 56 (2010) 139; Y.Xin, J.-G.Liu, Y.Zhou, W.Liu, J.Gao, Y.Xie, Y.Yin, Z.Zou, J.Power Sources 196 (2011) 1012; E.Yoo, T.Okada, T.Akita, M.Kohyama, I.Honma, J.Nakamura, J.Power Sources 196 (2011) 110) report that Graphene and Pt, Pd etc. form composite, can effectively reduce the oxidizing potential of methyl alcohol, show efficient electro-catalysis ability.But Graphene is easily reunited at water and in common are machine solvent, it is direct mixing method, coating method etc. that current using mineral carbon alkene comes modified electrode material to adopt more method, such as having reported, Chinese patent CN 101733094 A, CN101745384 A, CN 101814607 A take Graphene as carrier, directly supported platinum nano particle is prepared platinum/graphen type eelctro-catalyst, demonstrated the catalytic activity to methyl alcohol, but the method for this direct load has also limited the further application of Graphene.If can overcome its surperficial relative inertness state with water soluble polymer functional modification Graphene, strengthen water-soluble, change surface charge property and configuration of surface, retain higher electrocatalysis characteristic and good electronic conductivity, to prepare nano composite membrane by methods such as self assemblies layer by layer and for modified electrode with other functional component as POMs simultaneously.
Summary of the invention
The object of the invention is first by functional modification Graphene and polyoxometallate, on electrode, by layer upon layer electrostatic self assembly, to obtain the composite membrane that outermost layer is functional modification Graphene or polyoxometallate, take composite membrane as the electro-deposition of basalis original position obtains nano platinum particle again, make the anodic composite film catalyst that can be used for DMFC being formed by Pt nano particle, functional modification Graphene and polyoxometallate.Graphite oxide is to take native graphite as raw material: with reference to Adv.Funct.Mater.2010, the disclosed technology of 20,3366-3372 makes by improving Hummers method.
For realizing the technical scheme of object employing of the present invention, be:
1, the preparation of functional modification Graphene
Get graphite oxide and be dissolved in deionized water, after ultrasonic 30～40min, form uniform dispersion, add high molecular weight water soluble polymer, 50～80 ℃ of backflow 12h under stirring condition, are cooled to and drip hydrazine hydrate vigorous stirring 5min simultaneously after room temperature; Be warming up to after 90～110 ℃, the 12～24h that refluxes under stirring condition, centrifugation products therefrom, adds the functional modification graphene solution that water preparation obtains 0.5～1mg/mL, standby.
Described graphite oxide is dissolved in deionized water, is according to mass ratio, to be 1:2000 ratio is carried out.
The described high molecular weight water soluble polymer that adds is to be that 1～30 ︰ 1 ratio is carried out according to the mass ratio of high molecular weight water soluble polymer and graphite oxide.
Described high molecular weight water soluble polymer is polymine (PEI), diallyl dimethyl ammoniumchloride (PDDA) or PVP (PVP).
2, glass-carbon electrode substrate pretreatment
Glass-carbon electrode substrate is used first successively to α-Al of 1.0,0.3 and 0.05 μ m
2o
3powder polishing, then ultrasonic cleaning 10min in ethanolic solution and distilled water successively; Glass-carbon electrode substrate after cleaning is placed in to 0.5molL
-1h
2sO
4in solution, control potential range-0.25V～1.25V and carry out cycle potentials scanning, until obtain stable standard cycle voltammogram, standby.
3, composite membrane self assembly:
To be placed in 0.5mol/L H through pretreated glass-carbon electrode substrate
2sO
4in-0.8～1.0V potential range in scan round until obtain stable response curve, then by glass-carbon electrode deionized water rinsing for substrate, slowly dry up with nitrogen;
The glass-carbon electrode substrate drying up is immersed to 20min in pre-prepared functional modification graphene solution, obtain the glass-carbon electrode substrate of modification, at glass-carbon electrode substrate, modify last layer functional modification Graphene;
Take out the glass-carbon electrode substrate of having modified, with deionized water rinsing, and slowly dry up with nitrogen, after drying up, immerse again in the solution of 10mmol/L polyoxometallate, soak 20min, modify last layer polyoxometallate;
The glass-carbon electrode substrate of modifying last layer polyoxometallate is alternately immersed in functional modification graphene solution and polyoxometallic acid salting liquid, and the number of times alternately immersing is to make the MULTILAYER COMPOSITE membrane glass-carbon electrode substrate that outermost layer is functional modification Graphene or polyoxometallate for 1-4 time.
Described polyoxometallate molecular formula is [PX
12o
40]
n-, wherein: X
12=Mo
12, W
12, CuMo
11, PdMo
11, CuW
11or PdW
11.
4, nano platinum particle electro-deposition
Under three-electrode system, the MULTILAYER COMPOSITE membrane glass-carbon electrode substrate of take is working electrode, and platinum post is to electrode, and Ag|AgCl is reference electrode, at the H of 0.1～1.0mmol/L
2ptCl
6acid solution in take constant potential as-0.6～-0.1V, sedimentation time is original position electro-deposition reduction Pt nano particle under 200～1200s condition, make the anodic composite film catalyst that contains Pt nano particle, i.e. Pt nano particle/functional modification Graphene/polyoxometallate film catalyst.
Described Ag|AgCl reference electrode, its electrolyte is saturated KCl solution.
Pt nano particle/functional modification Graphene/polyoxometallate film catalyst system of the present invention preparation first, can be used as the anode catalyst of DMFC, and compare with pure platinum catalyst, because the introducing of functional modification Graphene and polyoxometallate significantly improves the electro catalytic activity of film catalyst and resisting CO poison ability, and preparation method is simple, cost, is a kind of novel anode catalysts for direct methanol fuel cell.
Accompanying drawing explanation
Fig. 1 is the film catalyst Pt-after embodiment 1 platinum electrodeposition
nano-{ 2PEI-GN/2PMo
12x-ray photoelectron energy spectrogram.
Fig. 2 is the film catalyst Pt-after embodiment 1 platinum electrodeposition
nano-{ 2PEI-GN/2PMo
12scale be the scanning electron microscope (SEM) photograph of 1 μ m.
Fig. 3 is embodiment 2Pt-
nano-{ the CV curve map of the film modified electrode of 5PDDA-GN/4PPdW11} catalytic oxidation methyl alcohol in acid solution.
The specific embodiment
Embodiment 1
1, glass-carbon electrode substrate pretreatment:
Glass-carbon electrode substrate is used first successively to α-Al of 1.0,0.3 and 0.05 μ m
2o
3powder polishing, the ultrasonic 10min that cleans successively in ethanolic solution and distilled water then, at 0.5molL
-1h
2sO
4in solution, control potential range-0.25V～1.25V and carry out cycle potentials scanning, until obtain stable standard cycle voltammogram.
2, the preparation of PEI functional modification Graphene
Getting 0.05g graphite oxide is dissolved in 100mL deionized water, after ultrasonic 30min, form uniform dispersion, add 0.8g PEI, the lower 60 ℃ of backflow 12h of stirring condition, are cooled to room temperature and add 2 hydrazine hydrate vigorous stirring 5min, the lower 96 ℃ of backflow 12h of stirring condition, centrifugation goes out precipitation, and deionized water is washed to neutrality and obtained PEI functional modification Graphene, and Product Labeling is PEI-GN, add the solution that water preparation obtains 1mg/mL, standby.
3, composite membrane self assembly:
To be placed in 0.5mol/L H through pretreated glass-carbon electrode substrate
2sO
4in-0.8～1.0V potential range in scan round until obtain stable response curve.Then, with after deionized water rinsing, with nitrogen, slowly dry up, immersed 20min in the PEI-GN solution of 1mg/mL, taking-up deionized water rinsing, and slowly dry up with nitrogen, obtain modifying the glass-carbon electrode substrate of last layer PEI-GN.The modified glass-carbon electrode substrate drying up is immersed to 10mmol/L polyoxometallate H
3pMo
12o
40(0.5mol/L H
2sO
4for solvent) solution in, soak 20min, modify last layer PMo
12.Glass-carbon electrode substrate is successively alternately immersed to PEI-GN and PMo
12in solution, repeat alternately to immerse 1 time, can make outermost layer is PMo
12multilayer complex films { 2PEI-GN/2PMo
12glass-carbon electrode substrate.
4, nano platinum particle electro-deposition
Under three-electrode system, { 2PEI-GN/2PMo
12the film modified glass-carbon electrode substrate of MULTILAYER COMPOSITE is working electrode, and platinum post is to electrode, Ag | AgCl is reference electrode, at the H of 1.0mmol/L
2ptCl
6in acid solution, take constant potential as-0.2V, and sedimentation time is original position electro-deposition reduction nano platinum particle under 600s condition, makes film catalyst Pt-
nano-{ 2PEI-GN/2PMo
12.
Film catalyst Pt-after platinum electrodeposition
nano-{ 2PEI-GN/2PMo
12through x-ray photoelectron power spectrum, characterize, in spectrogram, there is Mo 3d, P 2p, O 1s, N 1s, the signal peak of C 1s, belongs to respectively PMo
12and PEI-GN, PMo is described
12be assembled in laminated film with PEI-GN.And the signal peak of Pt 4f is obvious especially in spectrogram, illustrate nano platinum particle also successful electro-deposition to composite membrane.The spectrogram of x-ray photoelectron power spectrum as shown in Figure 1.
Film catalyst Pt-after platinum electrodeposition
nano-{ 2PEI-GN/2PMo
12to show that Pt particle presents spherical for ESEM characterization result, and surface is crude a little, and particle size is about 0.3-0.7 μ m.Its result as shown in Figure 2.
The prepared complex film modified electrode electrocatalysis characteristic test of the present embodiment is carried out on CHI660 type electrochemical workstation (Shanghai Chen Hua instrument company).Condition of work is normal pressure, and operating temperature is 25 ℃, and methanol concentration is 0.5molL
-1.
By the film catalyst preparing, for the catalysis of DMFC (DMFC), compare with adopting pure platinum modified electrode catalyst, its catalysis methanol oxidation peak current is doubled, oxidation peak current potential has negative moving, and illustrates that catalytic activity is high, and anti-poisoning ability significantly strengthens.
Embodiment 2
1, glass-carbon electrode substrate pretreatment:
The preprocess method of glass-carbon electrode substrate is identical with embodiment 1.
2, the preparation of PDDA functional modification Graphene
Getting 0.10g graphite oxide is dissolved in 200mL deionized water, after ultrasonic 40min, form uniform dispersion, add 3.0gPDDA, the lower 80 ℃ of backflow 12h of stirring condition, be cooled to room temperature and add 2 hydrazine hydrate vigorous stirring 5min, the lower 110 ℃ of backflow 24h of stirring condition, obtain the grapheme modified solution of water-solubility functionization, after ultrasonic 30min, centrifugation goes out partly precipitated, solution is ultrasonic rear centrifugation precipitation again, obtain being uniformly dispersed and PDDA functional modification Graphene steady in a long-term in the aqueous solution, Product Labeling is PDDA-GN, concentration is the solution of 0.5mg/mL, standby.
3, composite membrane self assembly:
To be placed in 0.5mol/L H through pretreated glass-carbon electrode substrate
2sO
4in-0.8～1.0V potential range in scan round until obtain stable response curve.Then, by glass-carbon electrode substrate deionized water rinsing, with nitrogen, slowly dry up; The glass-carbon electrode substrate drying up is immersed to 20min in the PDDA-GN solution of pre-prepared 0.5mg/mL, modify last layer functional modification Graphene PDDA-GN; Take out the glass-carbon electrode substrate of having modified last layer functional modification Graphene, with deionized water rinsing, and slowly dry up with nitrogen, immerse 10mmol/L H
3pPdW
11o
40(0.5mol/L H
2sO
4for solvent) solution in, soak 20min, modify last layer PPdW
11.Glass-carbon electrode substrate is alternately immersed to PDDA-GN and PPdW
11in solution, then repeat said process 3.5 times, making outermost layer is the multilayer complex films { 5PDDA-GN/4PPdW of PDDA-GN
11.
4, nano platinum particle electro-deposition
Under three-electrode system, { 5PDDA-GN/4PPdW
11the film modified electrode of MULTILAYER COMPOSITE is working electrode, and platinum post is to electrode, Ag|AgCl is reference electrode, at the H of 0.25mmol/L
2ptCl
6in acid solution, take constant potential as-0.2V, and sedimentation time is original position electro-deposition reduction nano platinum particle under 400s condition, makes film catalyst Pt-
nano-{ 5PDDA-GN/4PPdW
11.
Electrocatalysis characteristic method of testing is with embodiment 1.By the film catalyst Pt-making
nano-{ 5PDDA-GN/4PPdW
11anode-catalyzed for DMFC (DMFC), compare with the pure platinum modified electrode catalyst of employing, its catalysis methanol oxidation peak current has improved 115%, oxidation peak current potential has negative moving, illustrate that catalytic activity is high, anti-poisoning ability significantly strengthens, and the CV curve of film modified electrode catalytic oxidation methyl alcohol in acid solution as shown in Figure 3.
Embodiment 3
1, glass-carbon electrode substrate pretreatment:
The preprocess method of glass-carbon electrode substrate is identical with embodiment 1.
2, the preparation of PEI functional modification Graphene
The preparation method of PEI functional modification Graphene is identical with embodiment 1.
3, composite membrane self assembly:
To be placed in 0.5mol/L H through pretreated electrode
2sO
4in-0.8～1.0V potential range in scan round until obtain stable response curve.Then use deionized water rinsing, with nitrogen, slowly dry up, immersed 20min in the PEI-GN solution of 1mg/mL, taking-up deionized water rinsing, and slowly dry up with nitrogen, obtain modifying the glass-carbon electrode substrate of last layer PEI-GN.The modified glass-carbon electrode substrate drying up is immersed to 10mmol/L polyoxometallate H
3pCuW
11o
40(0.5mol/LH
2sO
4for solvent) solution in, soak 20min, modify last layer PCuW
11.Glass-carbon electrode substrate is successively alternately immersed to PEI-GN and PCuW
11in solution, then repeat said process 1.5 times, making outermost layer is the multilayer complex films { 3PEI-GN/2PCuW of PEI-GN
11.
4, nano platinum particle electro-deposition
Under three-electrode system, with { 3PEI-GN/2PCuW
11the film modified electrode of MULTILAYER COMPOSITE is working electrode, and platinum post is to electrode, Ag|AgCl is reference electrode, at the H of 0.25mmol/L
2ptCl
6in acid solution, take constant potential as-0.2V, and sedimentation time is original position electro-deposition reduction nano platinum particle under 200s condition, makes film catalyst Pt-
nano-{ 3PEI-GN/2PCuW
11.
Electrocatalysis characteristic method of testing is with embodiment 1.By the film catalyst Pt-making
nano-{ 3PEI-GN/2PCuW
11anode-catalyzed for DMFC (DMFC), to compare with adopting pure platinum modified electrode catalyst, its catalysis methanol oxidation peak current has improved 87%, and oxidation peak current potential has negative moving, and illustrates that catalytic activity is high, and anti-poisoning ability significantly strengthens.
Embodiment 4
1, glass-carbon electrode substrate pretreatment:
The preprocess method of glass-carbon electrode substrate is identical with embodiment 1.
2, the preparation of PVP functional modification Graphene:
The preparation of PVP functional modification Graphene (PVP-GN) is identical with the synthetic method of PDDA-GN in embodiment 2.
3, carry the preparation of platinum composite membrane:
Pretreatment glass-carbon electrode substrate is placed in to 0.5mol/L H
2sO
4in-0.8～1.0V potential range in scan round until obtain stable response curve.Then, with after deionized water rinsing, nitrogen slowly dries up, and is immersed 20min in the PVP-GN solution of 0.5mg/mL, taking-up deionized water rinsing, and slowly dry up with nitrogen, obtain modifying the glass-carbon electrode substrate of last layer PVP-GN.Then under three-electrode system, the electrode that PVP-GN modifies is working electrode, and platinum post is to electrode, the saturated KCl solution of Ag|AgCl() be reference electrode, at the H of 1.0mmol/L
2ptCl
6acid solution in take constant potential as-0.2V, sedimentation time is original position electro-deposition reduction nano platinum particle under 1200s condition.By the electrode after platinum electrodeposition, be placed in 10mmolL again
-1h
3pW
12o
40(be labeled as PW
12) in, in-0.15V～0.7V potential range with 100mVs
-1sweep speed scan 40 weeks, by ethanolic solution and washed with de-ionized water, can make [PVP-GN/Pt-
nano/ PW
12] film catalyst.
Electrocatalysis characteristic method of testing is with embodiment 1.Anode-catalyzed by the film catalyst preparing for DMFC (DMFC), compare with adopting pure platinum modified electrode catalyst, its catalysis methanol oxidation peak current has improved 91%, and oxidation peak current potential has negative moving, illustrate that catalytic activity is high, anti-poisoning ability significantly strengthens.
Claims (5)
1. a preparation method for DMFC anodic composite film catalyst, is characterized in that:
1) preparation of functional modification Graphene
Getting graphite oxide is dissolved in deionized water; after ultrasonic 30～40 min, form uniform dispersion; add high molecular weight water soluble polymer; under stirring condition, heat up, reflux; under cooling rear dropping hydrazine hydrate vigorous stirring, heat up again, reflux; centrifugation, adds the functional modification graphene solution that water preparation obtains 0.5～1 mg/mL, standby;
2) glass-carbon electrode substrate pretreatment
By glass-carbon electrode α-Al for substrate
2o
3powder polishing, then ultrasonic cleaning 10 min in ethanolic solution and distilled water successively; Glass-carbon electrode substrate after cleaning is placed in to H
2sO
4in solution, control potential range and carry out cycle potentials scanning, standby;
3) composite membrane self assembly:
To be placed in H through pretreated glass-carbon electrode substrate
2sO
4in carry out scan round, and afterflush, dry up; The glass-carbon electrode substrate drying up is immersed to 20 min in pre-prepared functional modification graphene solution, obtain the glass-carbon electrode substrate of modifying; Take out the glass-carbon electrode substrate of having modified, then immerse in the solution of 10 mmol/L polyoxometallates, soak 20 min; Then alternately immerse in functional modification graphene solution and polyoxometallic acid salting liquid, the number of times alternately immersing is 1-4 time;
4) nano platinum particle electro-deposition
Under three-electrode system, the MULTILAYER COMPOSITE membrane glass-carbon electrode substrate of take is working electrode, and platinum post is to electrode, and Ag|AgCl is that reference electrode carries out electro-deposition, makes the anodic composite film catalyst that contains Pt nano particle;
Described polyoxometallate, molecular formula is [PX
12o
40]
n-, wherein: X
12=Mo
12or W
12;
Described high molecular weight water soluble polymer is to be that 1～30:1 ratio is carried out according to the mass ratio of high molecular weight water soluble polymer and graphite oxide;
Described high molecular weight water soluble polymer is polymine, diallyl dimethyl ammoniumchloride or PVP.
2. the preparation method of a kind of DMFC anodic composite film catalyst according to claim 1, it is characterized in that described graphite oxide is dissolved in deionized water, is according to the mass ratio of graphite oxide and deionized water, to be 1:2000 ratio is carried out.
3. the preparation method of a kind of DMFC anodic composite film catalyst according to claim 1, it is characterized in that described intensification, backflow, heat up again, reflux, its process is: 50～80 ℃ of 12 h that reflux under stirring condition, drip hydrazine hydrate vigorous stirring 5 min simultaneously after being cooled to room temperature; Be warming up to after 90～110 ℃, 12～24 h reflux under stirring condition again.
4. the preparation method of a kind of DMFC anodic composite film catalyst according to claim 1, is characterized in that potential range is-0.25 V～1.25V, H in the cycle potentials scanning described in the pretreatment of glass-carbon electrode substrate
2sO
4the concentration of solution is 0.5molL
– 1.
5. the preparation method of a kind of DMFC anodic composite film catalyst according to claim 1, is characterized in that, in the scan round described in composite membrane self assembly, potential range is-0.8～1.0 V, H
2sO
4the concentration of solution is 0.5 mol/L.
6. the preparation method of a kind of DMFC anodic composite film catalyst according to claim 1, is characterized in that described electro-deposition, is the H at 0.1～1.0 mmol/L
2ptCl
6acid solution in, take constant potential as-0.6～-0.1 V, sedimentation time is to carry out under 200～1200 s conditions.
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