CN102266770A - Preparation method of platinum/graphene nanometer electro-catalyst used for proton exchange membrane fuel cell - Google Patents
Preparation method of platinum/graphene nanometer electro-catalyst used for proton exchange membrane fuel cell Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 184
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- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 46
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 24
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 8
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- 238000000034 method Methods 0.000 claims abstract description 21
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- 239000010439 graphite Substances 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 97
- 239000003054 catalyst Substances 0.000 claims description 73
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 8
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- 230000008014 freezing Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
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- 210000004027 cell Anatomy 0.000 description 25
- 238000012360 testing method Methods 0.000 description 20
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- 229910021641 deionized water Inorganic materials 0.000 description 15
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
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- 230000010718 Oxidation Activity Effects 0.000 description 4
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- 238000002484 cyclic voltammetry Methods 0.000 description 3
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 239000010410 layer Substances 0.000 description 2
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- 239000002356 single layer Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- -1 platinum ion Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
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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
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Abstract
The invention relates to a preparation method of a platinum/graphene nanometer electro-catalyst used for a proton exchange membrane fuel cell. The preparation method comprises the following steps: ultrasonically dispersing a graphite oxide nanometer sheet into a reducing agent with weaker reduction capacity; adding a chloroplatinic solution and fully mixing; using sodium hydroxide to adjust pH value to 13; reducing for 2-6 hours at 70-160 DEG C; adding the reducing agent with stronger reduction capacity into the mixture; reducing for 1-15 hours at the temperature between room temperature and 120 DEG C; after cooling, using hydrochloric acid to adjust pH value to 3; and finally settling, filtering, cleaning, freezing and drying to obtain the platinum/graphene nanometer electro-catalyst. The platinum/graphene nanometer electro-catalyst prepared by using the method provided by the invention has the advantages that the platinum grains have smaller grain sizes, the grain size distribution is more concentrated, the loaded platinum grains are at the state of lower chemical valence, and the electrochemical catalytic activity is more excellent.
Description
Technical field
The present invention relates to the preparation of nano electro-catalytic agent material, relate in particular to Graphene as Proton Exchange Membrane Fuel Cells eelctro-catalyst of carrier and preparation method thereof.
Background technology
Graphene is a kind of by the tightly packed bi-dimensional cellular shape lattice structure carbonaceous material that forms of monolayer carbon atom, since finding to 2004, has received great concern on experimental science and pure science.Graphene is the outstanding material of present electric conductivity, and has huge specific area, higher carrier mobility speed and than characteristics such as high Young's modulus, ferromagnetism.Based on its special nanostructured and performance, grapheme material has demonstrated huge application potential at numerous areas such as electronics, optics, magnetics, biomedicine, catalysis, sensor, energy storage.
People such as Geim point out that in the Science magazine of delivering in 2009 Graphene is to have the material with carbon element that is less than 10 layers of graphite molecule layer structure, and the theoretical specific area of single-layer graphene can reach 2620m
2/ g, Given this it can provide more metal load byte; Simultaneously, Graphene shows very strong quantum effect, and electron motion speed can reach 1/300 of the light velocity in theory, has excellent electronic conduction ability.So Graphene can be used as the alternative materials of the excellence of fuel-cell catalyst carrier.
Calculate discovery by first principle, the platinum cluster can stably be carried on the Graphene surface, and the existence of Graphene can make carbon monoxide and the hydrogen energy of adsorption on the metal platinum catalyst reduce, and the reaction that more helps in the fuel cell takes place.In this simultaneously, since 2009 successively relevant for the act as a fuel experiment report appearance of cell catalyst carrier of the grapheme material after Graphene and the functionalization.Carbon magazine 2010 48 volume reported for 1124 pages adopt ethylene glycol be reducing agent prepare the Graphene platinum catalyst particle diameter in 5nm, and its electrochemically active specific surface area is about 36.27m
2/ g is than CNT platinum catalyst 33.43m
2The electrochemistry specific surface of/g is bigger.Simultaneously, the Graphene platinum catalyst demonstrates poison control centre CO in the methanol oxidation reaction is had better tolerance.Journal of the Electrochemical Society magazine 2010 157 volume B874 page or leaf has reported that platinum is dispersed in the Graphene of functionalization and a kind of new catalyst on the multi-wall carbon nano-tube composite material, is applied to that the battery power density can reach 540mV/cm on the fuel cell
2
By optimizing platinum the supporting of Graphene surface, thereby improve the nanometer electrical catalyst catalytic activity, based on some researchs in early stage, this part is operated in has report to occur in the world successively.2010 4 volumes of ACS Nano magazine, 547 beginnings of the page are inferior has reported that the synthetic high-quality Graphene of employing liquid chemical method is carrier platinum-palladium bimetal nano dendrite catalyst.Its result of study shows, one-step method reduction obtains in the Graphene platinum catalyst platinum grain and very easily reunites and disperse inhomogeneous, when Graphene is catalyst carrier, platinum grain is formed pine-tree structure on the surface of palladium particle carry out the secondary dispersion, can obtain the littler platinum nano catalyst of particle.This catalyst has the much higher methanol oxidation electro catalytic activity of more business-like carbon supported platinum catalyst.2011 196 volumes of Journal of Power Sources magazine have been reported the influence of annealing in process to the Graphene platinum catalyst for 1012 pages.Be to carry out annealing in process after reducing agent prepares the Graphene platinum catalyst with the sodium borohydride, the eelctro-catalyst catalytic performance is significantly improved.Result of study shows that the peak current that carries out the catalyst methanol oxidation reaction of annealing in process after the reduction has again improved 3.5 times.Analyze by x-ray photoelectron power spectrum (XPS), this might be that high annealing has strengthened results of interaction between platinum and the Graphene.
Summary of the invention
The objective of the invention is to prepare a kind of used in proton exchange membrane fuel cell platinum/graphen catalyst, wherein the platinum carrying capacity is 10-40wt%.This catalyst uses Graphene to be carrier, utilizes distinctive two-dimentional ductility of Graphene and quantum effect, to improve the performance of fuel-cell catalyst.By graphite oxide and chloroplatinic acid are carried out ultrasonic blend, at first make spent glycol or formaldehyde carry out first step reduction as reducing agent, adopt sodium borohydride or hydrazine hydrate to carry out the reduction of second step again as reducing agent, utilize two step reduction method to optimize activity of such catalysts, have the more catalyst of fuel batter with proton exchange film of high catalytic activity thereby prepare.
Technical scheme of the present invention is as follows:
A kind of method for making of used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst, it comprises the following steps:
The raw material graphite oxide is to prepare according to traditional Hummers method among the present invention, and concrete preparation method is as follows: the natural flaky graphite dispersed with stirring of 3g in the 66ml 98wt% concentrated sulfuric acid, is added 3g sodium nitrate and stirs under the ice-water bath condition; Slowly add 12g potassium permanganate again and react, about 1 hour, stirred 2 hours except that being warming up to 45 ℃ behind the ice bath; Add 120ml water, reaction temperature is risen to 90 ℃, be incubated 1 hour; Add 400ml water and 12ml 30wt% hydrogen peroxide solution cessation reaction then; Use deionized water, aqueous hydrochloric acid solution and ethanol centrifuge washing 2 times at last respectively, 50 ℃ of dryings obtained the graphite oxide film in 24 hours, and it is last stand-by to pulverize.
Among the preparation method of a kind of used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst of the present invention, the two step reduction method that adopts, the different of under reducing agent effect not of the same race platinum ion and graphite oxide rate of reduction have been considered, and the strong and weak difference of different reducing agent reducing powers, make that platinum grain has kept smaller particle size in the platinum/graphene nano electro-catalyst for preparing, having more concentrated particle diameter simultaneously distributes, and the platinum grain of load presents lower chemical valence state, has more excellent electrochemical catalysis activity.It is that electro-chemical activity, specific area, methanol oxidation reaction and oxygen reduction reaction electro catalytic activity or catalyst stability all have significantly and improve that the more conventional one-step method of used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst for preparing among the present invention prepares platinum/graphen catalyst.
Description of drawings
Fig. 1 is the cyclic voltammogram comparison that embodiment 1, Comparative Examples 1 and Comparative Examples 2 obtain platinum/graphene nano electro-catalyst.
Fig. 2 is that embodiment 1, Comparative Examples 1 and Comparative Examples 2 obtain platinum/graphene nano electro-catalyst catalysis methanol oxidation reaction current ratio.
Fig. 3 is that embodiment 1, Comparative Examples 1 and Comparative Examples 2 obtain platinum/graphene nano electro-catalyst catalytic oxidation-reduction kinetic current relatively.
Fig. 4 is that embodiment 1, Comparative Examples 1 and Comparative Examples 2 obtain platinum/graphene nano electro-catalyst stability relatively.
Fig. 5 is respectively Comparative Examples 1(a), Comparative Examples 2(b) and embodiment 1(c) obtain the contrast that distributes of platinum/graphene nano electro-catalyst stereoscan photograph and particle diameter.
Fig. 6 is embodiment 2(a), embodiment 3(b) and embodiment 4(c) and embodiment 5(d) the 2 footworks reduction preparation platinum/graphen catalyst stereoscan photograph that obtains.
Fig. 7 is respectively Comparative Examples 1(a), Comparative Examples 2(b) and embodiment 1(c) obtain Pt(4f in the platinum/graphene nano electro-catalyst) XPS spectrum figure result relatively.
The specific embodiment
The following examples help further to elaborate the present invention, and should not be interpreted as limiting the scope of the invention.
The detection method of the electrochemically active specific surface area of the used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst that the present invention obtains, methanol oxidation reaction and test of oxygen reduction reaction electro catalytic activity and catalyst stability is finished by testing in the standard three-electrode system.Adopt the platinum electrode conduct to electrode, saturated calomel electrode (SCE) is as reference electrode, and diameter is that the glass-carbon electrode of 5mm is a working electrode, and electrolyte is the 0.5M sulfuric acid solution.Test is carried out on the Princeton2273 electrochemical workstation, and specific operation process is: accurately take by weighing the 5mg catalyst fines, add 100 μ L 5wt% Nafion
(Du Pont company) solution, ultrasonic being scattered in the 900 μ L ethanolic solutions.Pipetting 10 μ L drips in glass-carbon electrode surface, drying at room temperature.
Electrochemically active specific surface area adopts the cyclic voltammetric test to obtain, and feeds N in the electrolyte solution before the test
20.5 hour, in 0.042 to 1.442V (NHE) interval, carry out repeatedly cyclic voltammetry scan with the sweep speed of 20mV/s, stable up to curve.Last lap cyclic voltammetric data computation is obtained corresponding electrochemically active specific surface area.
The test of catalysis methanol oxidation activity is carried out in the electrolyte solution that contains 0.5M methyl alcohol, feeds N in the electrolyte solution before the test
20.5 hour, in 0.042 to 1.242V (NHE) interval, carry out repeatedly cyclic voltammetry scan with the sweep speed of 20mV/s, stable up to curve.
Feed O in the electrolyte solution before the test of catalytic oxidation-reduction reactivity
20.5 hour, in 1.242 to 0.242V (NHE) interval, carry out electric potential scanning at a slow speed with the sweep speed of 5mV/s, this moment, the rotating speed of working electrode was 2500rpm.
Feed N in the electrolyte solution before the electrochemical stability property testing
20.5 hour, measuring current time graph under 0.842V (NHE) constant-pressure conditions.
Embodiment 1:2 stage reduction method
To be dispersed in ultrasonic about 2 hours of 75mg graphite oxide nanometer sheet in the 30mL ethylene glycol with ultrasonic cell disruptor, the ethylene glycol solution that adds the 1.7mL0.038mol/L chloroplatinic acid then, making platinum carrying capacity in platinum/graphen catalyst is 20wt%, fully ultrasonic mixing.Regulate pH value to 13 with 2M NaOH ethylene glycol solution, reduction is 3 hours in 155 ℃ of oil baths; Reaction temperature is reduced to 80 ℃ then, add 250 μ g hydrazine hydrates, reacted 1 hour, be cooled to room temperature subsequently, regulate pH value to 3, add deionized water 50mL sedimentation 3 hours with aqueous hydrochloric acid solution, suction filtration then, and with the washing of 80 ℃ deionized water for several times, about 12 hours of freeze drying obtains used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst of the present invention.This catalyst carries out the cyclic voltammetric test result and sees Fig. 1; The test result of catalysis methanol oxidation activity is seen Fig. 2; The test result of catalytic oxidation-reduction reactivity is seen Fig. 3; The electrochemical stability test result is seen Fig. 4.
Pt(4f in the platinum/graphen eelctro-catalyst of present embodiment) XPS characterization result is seen Fig. 7 c.Its stereoscan photograph is seen Fig. 5 c.
Embodiment 2:2 stage reduction method
To be dispersed in ultrasonic about 2 hours of 75mg graphite oxide nanometer sheet in the 30ml ethylene glycol with ultrasonic cell disruptor, the ethylene glycol solution that adds 1.7mL 0.038mol/L chloroplatinic acid then, making platinum carrying capacity in platinum/graphen catalyst is 20wt%, fully ultrasonic mixing.Regulate pH value to 13 with 2M NaOH ethylene glycol solution, reduction is 3 hours in 155 ℃ of oil baths; Then reaction temperature is reduced to room temperature, add the 75mg sodium borohydride, reacted 12 hours, regulate pH value to 3 with aqueous hydrochloric acid solution subsequently, add deionized water 50mL sedimentation 3 hours, suction filtration then, and with 80 ℃ deionized water washing several, about 12 hours of freeze drying obtains used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst of the present invention.The catalyst that its performance makes with embodiment 1.Its stereoscan photograph is seen Fig. 6 a.
Embodiment 3:2 stage reduction method
To be dispersed in ultrasonic about 2 hours of 75mg graphite oxide nanometer sheet in the 150mL formaldehyde with ultrasonic cell disruptor, the ethylene glycol solution that adds 1.7mL 0.038mol/L chloroplatinic acid then, making platinum carrying capacity in platinum/graphen catalyst is 20wt%, fully ultrasonic mixing.Regulate pH value to 13 with 2M NaOH ethylene glycol solution, reduction is 1 hour in 80 ℃ of oil baths; And then add 250 μ g hydrazine hydrates, reacted 1 hour, be cooled to room temperature subsequently, regulate pH value to 3 with aqueous hydrochloric acid solution, add deionized water 50mL sedimentation 3 hours, suction filtration then, and with 80 ℃ deionized water washing several, about 12 hours of freeze drying obtains used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst of the present invention.The catalyst that its performance makes with embodiment 1.Its stereoscan photograph is seen Fig. 6 b.
Embodiment 4:2 stage reduction method
To be dispersed in ultrasonic about 2 hours of 75mg graphite oxide nanometer sheet in the 150mL formaldehyde with ultrasonic cell disruptor, the ethylene glycol solution that adds 1.7mL 0.038mol/L chloroplatinic acid then, making platinum carrying capacity in platinum/graphen catalyst is 20wt%, fully ultrasonic mixing.Regulate pH value to 13 with 2M NaOH ethylene glycol solution, reduction is 1 hour in 80 ℃ of oil baths; Then reaction temperature is reduced to room temperature, add the 75mg sodium borohydride, reacted 12 hours, regulate pH value to 3 with aqueous hydrochloric acid solution subsequently, add deionized water 50mL sedimentation 3 hours, suction filtration then, and with 80 ℃ deionized water washing several, about 12 hours of freeze drying obtains a kind of used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst.The catalyst that its performance makes with embodiment 1.Its stereoscan photograph is seen Fig. 6 c.
Embodiment 5:2 stage reduction method
To be dispersed in ultrasonic about 2 hours of 75mg graphite oxide nanometer sheet in the 30ml ethylene glycol with ultrasonic cell disruptor, the ethylene glycol solution that adds 3.4mL 0.038mol/L chloroplatinic acid then, making platinum carrying capacity in platinum/graphen catalyst is 40wt%, fully ultrasonic mixing.Regulate pH value to 13 with 2M NaOH ethylene glycol solution, reduction is 3 hours in 155 ℃ of oil baths; Reaction temperature is reduced to 80 ℃ then, add 250 μ g hydrazine hydrates, reacted 1 hour, be cooled to room temperature subsequently, regulate pH value to 3, add deionized water 50mL sedimentation 3 hours with aqueous hydrochloric acid solution, suction filtration then, and with the washing of 80 ℃ deionized water for several times, about 12 hours of freeze drying obtains used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst of the present invention.Its stereoscan photograph is seen Fig. 5 d.
Comparative Examples 1: reduction of ethylene glycol method
To be dispersed in ultrasonic about 2 hours of 75mg graphite oxide nanometer sheet in the 30ml ethylene glycol with ultrasonic cell disruptor, the ethylene glycol solution that adds 1.7mL 0.038mol/L chloroplatinic acid then, making platinum carrying capacity in platinum/graphen catalyst is 20wt%, fully ultrasonic mixing.Regulate pH value to 13 with 2M NaOH ethylene glycol solution, reduction is 3 hours in 155 ℃ of oil baths, be cooled to room temperature then, regulate pH value to 3 with aqueous hydrochloric acid solution, add deionized water 50mL sedimentation 3 hours, suction filtration then, and with 80 ℃ deionized water washing several, about 12 hours of freeze drying obtains a kind of used in proton exchange membrane fuel cell platinum/graphen catalyst.This catalyst carry out cyclic voltammetric test (the results are shown in Figure 1), catalysis methanol oxidation activity test (the results are shown in Figure 2), catalytic oxidation-reduction reactivity test (the results are shown in Figure 3), electrochemical stability property testing (the results are shown in Figure 4) and carry out XPS sign (the results are shown in Figure 7a).Its stereoscan photograph is seen Fig. 5 a.
Comparative Examples 2: hydrazine hydrate reduction method
To be dispersed in ultrasonic about 2 hours of 75mg graphite oxide nanometer sheet in the 30ml water with ultrasonic cell disruptor, the ethylene glycol solution that adds 1.7mL 0.038mol/L chloroplatinic acid then, making platinum carrying capacity in platinum/graphen catalyst is 20wt%, fully ultrasonic mixing.Regulate pH value to 13 with 2M NaOH ethylene glycol solution, add 250 μ g hydrazine hydrates, reductase 12 hour in 80 ℃ of water-baths, be cooled to room temperature then, regulate pH value to 3, add deionized water 50mL sedimentation 3 hours with aqueous hydrochloric acid solution, suction filtration then, and with the washing of 80 ℃ deionized water for several times, about 12 hours of freeze drying obtains a kind of used in proton exchange membrane fuel cell platinum/graphen catalyst.This catalyst carry out cyclic voltammetric test (the results are shown in Figure 1), catalysis methanol oxidation activity test (the results are shown in Figure 2), catalytic oxidation-reduction reactivity test (the results are shown in Figure 3), electrochemical stability property testing (the results are shown in Figure 4) and carry out XPS sign (the results are shown in Figure 7b).Its stereoscan photograph is seen Fig. 5 b.
2 footworks reduction of the present invention obtains the comparison that platinum/graphen catalyst and ethylene glycol or the reduction of hydrazine hydrate 1 footwork obtain catalyst:
Fig. 1 has illustrated that electrochemically active specific surface area that the reduction of 2 footworks obtains platinum/graphen catalyst obtains catalyst than ethylene glycol or the reduction of hydrazine hydrate 1 footwork and obviously increases.Wherein, to obtain the catalyst electrochemically active specific surface area be 63.9m for 2 footworks reduction
2/ g, ethylene glycol and the reduction of hydrazine hydrate 1 footwork obtain the catalyst electrochemically active specific surface area and are respectively 40.3m
2/ g and 1.4m
2/ g.
Fig. 2 has illustrated that methanol oxidation reaction electro catalytic activity that the reduction of 2 footworks obtains platinum/graphen catalyst obtains catalyst than ethylene glycol or the reduction of hydrazine hydrate 1 footwork and obviously increases.Wherein, to obtain catalyst methanol oxidation peak current be 299.3mA mg for 2 footworks reduction
-1Pt, ethylene glycol and the reduction of hydrazine hydrate 1 footwork obtain catalyst methanol oxidation peak current and are respectively 181.5mA mg
-1Pt and 93.4mA mg
-1Pt.
Fig. 3 has illustrated that oxygen reduction reaction electro catalytic activity that the reduction of 2 footworks obtains platinum/graphen catalyst obtains catalyst than ethylene glycol or the reduction of hydrazine hydrate 1 footwork and obviously increases.Wherein, the take-off potential that the reduction of 2 footworks obtains the catalyst oxygen reduction reaction is that 0.983V, half wave potential are 0.669V, and take-off potential and half wave potential that ethylene glycol and the reduction of hydrazine hydrate 1 footwork obtain the catalyst oxygen reduction reaction are respectively 0.953V, 0.630V and 0.893V and 0.594V.
Fig. 4 has illustrated that the reduction of 2 footworks obtains platinum/graphen catalyst and obtains catalyst obviously raising of stability under the 0.842V current potential than ethylene glycol or the reduction of hydrazine hydrate 1 footwork.2 footworks make catalyst current attenuation speed and significantly are lower than 1 footwork and make catalyst, illustrate that 2 footworks prepare the platinum/graphen eelctro-catalyst and are more suitable for being used for Proton Exchange Membrane Fuel Cells.
Fig. 5 has illustrated that 2 footworks reduction obtains platinum/graphen catalyst and obtains the littler and particle diameter of catalyst granules than ethylene glycol or the reduction of hydrazine hydrate 1 footwork and distribute more concentrated.Wherein 2 footworks and reduction of ethylene glycol prepare that the particle diameter of platinum grain is about 2 to 3 nanometers in the platinum/graphen catalyst, and 2 footworks prepare catalyst platinum grain particle diameter and distribute more concentrated; Hydrazine hydrate reduction prepares that the particle diameter of platinum grain is about 20 to 40 nanometers in the catalyst.
Fig. 6 has illustrated that 2 footworks reduction prepares that the platinum grain particle diameter is about 2 to 3 nanometers in the platinum/graphen catalyst.
Fig. 7 prepares Pt(4f in the platinum/graphen eelctro-catalyst for embodiment 1 and Comparative Examples 1) the XPS characterization result, by XPSPEAK software XPS spectrum figure is carried out the swarming match and obtains the result and show that the reduction of 2 footworks obtains Pt in the platinum/graphen catalyst
0, Pt
2+And Pt
4+The ratio that accounts for the Pt total amount is respectively 56.8%, 29.0% and 14.2%, wherein Pt
0Content is than Comparative Examples 1 high about 7%.
Claims (1)
1. the method for making of a used in proton exchange membrane fuel cell platinum/graphene nano electro-catalyst is characterized in that comprising the following steps:
Step 1. is dispersed in the more weak reducing agent of 20-200mL reducing power the graphite oxide nanometer sheet is ultrasonic, add platinum acid chloride solution then, fully mix, obtain the mixture of graphite oxide nanometer sheet and chloroplatinic acid after ultrasonic, platinum this moment carrying capacity in platinum/graphen catalyst is 10-40wt%, regulate pH value to 13 with NaOH, reduced 1-5 hour down at 70-160 ℃, described more weak reducing agent is ethylene glycol or formaldehyde;
Step 2. adds the stronger reducing agent of 100 μ g-100mg reducing powers again in mixture, room temperature-120 ℃ following reduction 1-15 hour, after the cooling, with salt acid for adjusting pH value to 3, through sedimentation, filtration, washing, freeze drying, obtain platinum/graphene nano electro-catalyst, described stronger reducing agent is hydrazine hydrate or sodium borohydride.
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