CN101259410A - Method for preparing platinum catalyst by electrodeposition - Google Patents

Method for preparing platinum catalyst by electrodeposition Download PDF

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CN101259410A
CN101259410A CNA2008101040180A CN200810104018A CN101259410A CN 101259410 A CN101259410 A CN 101259410A CN A2008101040180 A CNA2008101040180 A CN A2008101040180A CN 200810104018 A CN200810104018 A CN 200810104018A CN 101259410 A CN101259410 A CN 101259410A
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platinum
electrode
catalyst
electrodeposition
carbon
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CN101259410B (en
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王新东
李晶晶
叶锋
王永亮
王同涛
苗睿瑛
薛方勤
刘芸
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University of Science and Technology Beijing USTB
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    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation of a platinum catalyst of a direct methanol fuel cell, which adopts a method of electrodepositing and carries out pulse electrodepositing on platinum by two steps, namely a larger current is adopted for forming a crystal nucleus in step I; a small current is adopted for the growing the crystal nucleus in step II; the grain diameter of the prepared catalyst can be reduced through changing the applied electric signal; thereby leading the formed platinum grains to be more dispersive and have a higher covering rate and a larger specific surface; thereby reducing the platinum loading capacity of unit area of the electrodes, improving utilization rate and activity and simultaneously reducing the cost of the catalyst. The method is simple and controllable to be applied. The prepared platinum catalyst can not only be applied to the direct methanol fuel cell, but also can be applied to other fuel cells as catalysts. Besides, the method can be expanded and applied to platinum-ruthenium codeposition and other multi-metal codeposition.

Description

A kind of method of preparing platinum catalyst by electrodeposition
Technical field
The present invention relates to fuel cell field and Preparation of Catalyst field, relate in particular to DMFC Preparation of catalysts method based on platinum.
Background technology
DMFC (DMFC) has energy conversion efficiency height, pollution-free, noiselessness, system architecture is simple, specific energy is high and fuel carries and replenishes advantage such as convenient and receive much attention.One of critical material of DMFC is an electrode catalyst, its active performance that directly influences battery.The used eelctro-catalyst of DMFC all is main component with platinum at present, but platinum is noble metal, and scarcity of resources is because its utilization rate and the active not high requirement that does not also reach the DMFC commercialization.The residing position of catalyst platinum particles must be the zone that can touch reactant, electronic conductor and proton conductor simultaneously, be the phase reaction district, because only could guarantee the diffusion of effective gas and water and proton and electronics spreading out of and import into from the catalytic reaction position in the phase reaction district.Adopt in the electrode of traditional chemical synthesis process preparation, many platinum particles are owing to not becoming nonactive Pt in the phase reaction district.In order to overcome above shortcoming, improve the utilization rate of noble metal, adopt the Pt of prepared by electrodeposition only to be deposited in the zone that has electron conduction and proton conductive simultaneously.This process can be avoided the loss of active platinum position, thereby makes the Pt that is deposited be effective catalyst, has improved the noble metal utilization rate, i.e. the catalytic activity of unit mass noble metal catalyst Pt, and then reduced the cost of electrode.As Kyoung Hwan Choi, et.al., Electrode fabrication for proton exchange membrane fuel cells by pulse electrodeposition, the report of J.Power Sources 75 (1998) 230, but adopt two electrode systems to carry out pulse electrodeposition and prepare platinum catalyst, exist with platinum as anode cost height, the shortcoming that controllability is not high.And for example in the invention of CN1947835A " a kind of pulse electrodeposition prepares the method for DMFC with catalyst ", proposed Pt directly is deposited on method on activated carbon black/ion emulsion carriers, though the methanol electro-oxidizing-catalyzing activity higher slightly than commercial catalyst arranged, but particle size is in 100～300nm scope, and dispersiveness and coverage rate are not high, improve its catalysis methanol electroxidation performance, particle size is still waiting to reduce, dispersed and coverage rate has much room for improvement, and activity remains further to be strengthened.
Summary of the invention
The objective of the invention is to remedy the deficiency of said method, by dividing two stages to carry out pulse electrodeposition platinum, promptly the I stage adopts big electric current to be used for nucleus formation, and the II stage adopts little electric current to be used for nuclei growth, thereby the platinum particles of formation is disperseed more, coverage rate is higher, and yardstick further reduces, and specific area is bigger, and then the platinum load amount of reduction unit are electrode, improve the utilization rate and the activity of platinum, reduce the cost of catalyst simultaneously, application process is simple, controlled.
The present invention includes following implementation step:
1, the configuration ethanol that contains active carbon with
Figure A20081010401800041
Mixed liquor adds 5～8 milligrams ratio according to every milliliter of ethanol, and the active carbon Vulcan XC-72 of acidified processing is placed ethanol, adds again
Figure A20081010401800042
The ultrasonic dispersion of solution (5wt.%) 30～60 minutes forms the carbon slurry, guarantees
Figure A20081010401800043
The mass percent of solution and alcohol suspension is 100: 1～100: 5;
2, pipetting above-mentioned carbon slurry 150～300 μ L according to every square centimeter drips on the catalyst matrix surfaces such as the glass carbon handled well, graphite, carbon paper, carbon cloth, after treating that ethanol evaporation is intact, electrode in 50 ℃～70 ℃ vacuum drying 4～10h, is made employed working electrode in the electrodeposition process.
3, by working electrode, electrode, reference electrode are formed three-electrode system, wherein working electrode is the electrode that step 2 makes, and is platinum electrode to electrode, and reference electrode is saturated calomel electrode (SCE), and electrolyte is for containing 0～10 -3The 0.5molL of mM additive -1H 2SO 4With 0.5～2mmolL -1H 2PtCl 6Mixed solution, pulse electrodeposition divides two stages to carry out pulse electrodeposition platinum, the I stage is at big peak current density 12～36mAcm -2Deposit 30～120s, the II stage is adopted little peak current density 4～10mAcm -2The make-and-break time ratio t of electric current Off/ t OnBe 1.5～6: 1, total deposition electric weight is 1～2.5Ccm -2Electrodeposition temperature is 20～60 ℃.In solution, feed argon gas in the electrodeposition process.
The optimal selection of additive is 10 -5～10 -3MM, wherein additive is selected from a kind of in polyethylene glycol (PEG), lead acetate (LA), polyvinylpyrrolidone (PVP), the citric acid.
The invention has the advantages that and need not to change process, as long as the crystal grain of the catalyst that the signal of telecommunication that applies by change just can reduce to make, thereby the platinum particles of formation is disperseed more, coverage rate is higher, specific area is bigger, and then has reduced the platinum load amount of unit are electrode, has improved its utilization rate and activity, reduced the cost of catalyst simultaneously, application process is very simple.Prepared platinum catalyst not only can be applied to DMFC, can also be applied to other fuel-cell catalyst.In addition, this method can expand to platinum ruthenium codeposition and other multi-element metal codeposition.
Description of drawings
Fig. 1 amplifies 50,000 times ESEM shape appearance figure for example 2 synthetic catalyst.
Fig. 2 amplifies 50,000 times ESEM shape appearance figure for example 3 synthetic catalyst.
Fig. 3 is the cyclic voltammetry curve of the methyl alcohol electrochemical catalytic oxidization of the synthetic catalyst of example 1.
Fig. 4 is the cyclic voltammetry curve of the methyl alcohol electrochemical catalytic oxidization of the synthetic catalyst of example 2.
Fig. 5 is the cyclic voltammetry curve of the methyl alcohol electrochemical catalytic oxidization of the synthetic catalyst of example 3.
Fig. 6 is not for there being the segmentation electro-deposition, and peak current density is constant to be 6mAcm -2The cyclic voltammetry curve of the methyl alcohol electrochemical catalytic oxidization of the synthetic platinum catalyst of pulse electrodeposition under the condition.
The specific embodiment
At 0.5molL -1H 2SO 4+ 1.0molL -1CH 3In the OH solution, between the current potential 0 to 0.75V, sweep fast 10mVs -1Carry out the cyclic voltammetric test.The argon gas that carries out logical 20min in the cyclic voltammetry experiment forward direction electrolyte is to eliminate the influence of dissolved oxygen in the solution.Get continuous three all curves and overlap later cyclic voltammetry curve.Probe temperature is 30 ℃.The electric current of answering by the different electrode pairs under the same potential relatively comes the chemical property of the electrode of prepared by electrodeposition under the comparison different condition.
Embodiment 1:
Weighing 50mg places 10mL ethanol through the Vulcan of acidification XC-72, adds 100 μ L's The ultrasonic dispersion of solution (5wt.%, density is 45mgNafion/mL) 60 minutes mixes, and forms the carbon slurry,
Figure A20081010401800052
The mass percent of solution and alcohol suspension is 100: 1; Get 75 μ L and drip to glass-carbon electrode (the area 0.28cm that handles well 2) on the surface; After treating that ethanol evaporation is intact, with 50 ℃ of vacuum drying 7h of electrode, making employed working electrode in the electrodeposition process, is platinum electrode to electrode, and reference electrode is saturated calomel electrode (SCE), and the following stated current potential is all with respect to SCE.Electrolyte is 0.5molL -1H 2SO 4+ 2.0mmolL -1H 2PtCl 6Pulse electrodeposition divides two stages to carry out pulse electrodeposition platinum, and the I stage is at peak current density 12mAcm -2Deposit 120s, the peak current density in II stage are 8mAcm -2, total deposition electric weight is 1.2Ccm -2, the make-and-break time ratio t of electric current Off/ t OnBe 300ms: 100ms, electrodeposition temperature is 20 ℃.In solution, feed argon gas in the electrodeposition process.
Embodiment 2:
Weighing 40mg places 5mL ethanol through the Vulcan of acidification XC-72, adds 200 μ L's
Figure A20081010401800053
The ultrasonic dispersion of solution (5wt.%, density is 45mgNafion/mL) 40 minutes mixes, and forms the carbon slurry,
Figure A20081010401800054
The mass percent of solution and alcohol suspension is 100: 4; Get 75 μ L and drip to graphite electrode (the area 0.5cm that handles well 2) on the surface; After treating that ethanol evaporation is intact, with 60 ℃ of vacuum drying 5h of electrode, making employed working electrode in the electrodeposition process, is platinum electrode to electrode, and reference electrode is saturated calomel electrode (SCE).Electrolyte is 0.5molL -1H 2SO 4+ 0.5mmolL -1H 2PtCl 6Pulse electrodeposition divides two stages to carry out pulse electrodeposition platinum, and the I stage is at peak current density 36mAcm -2Deposit 60s, the peak current density in II stage are 6mAcm -2, total deposition electric weight is 1.2Ccm -2, the make-and-break time ratio t of electric current Off/ t OnBe 4s: 1s, electrodeposition temperature is 50 ℃.In solution, feed argon gas in the electrodeposition process.Make the nanoscale platinum catalyst of high dispersive, as shown in Figure 1.Block Pt particle about the about 100nm of diameter, specific area is very big, the coverage rate height.
Embodiment 3:
Weighing 50mg places 10mL ethanol through the Vulcan of acidification XC-72, adds 200 μ L's
Figure A20081010401800055
The ultrasonic dispersion of solution (5wt.%, density is 45mgNafion/mL) 30 minutes mixes, and forms the carbon slurry,
Figure A20081010401800056
The mass percent of solution and alcohol suspension is 100: 2; Getting 100 μ L drips on the graphite electrode surface of handling well; After treating that ethanol evaporation is intact, with 60 ℃ of vacuum drying 5h of electrode, making employed working electrode in the electrodeposition process, is platinum electrode to electrode, and reference electrode is saturated calomel electrode (SCE).Electrolyte is 0.5molL -1H 2SO 4+ 1.0mmolL -1H 2PtCl 6+ 10 -5MmolL -1PEG (molecular weight is 400).Pulse electrodeposition divides two stages to carry out pulse electrodeposition platinum, and the I stage is at peak current density 24mAcm -2Deposit 90s, the peak current density in II stage are 10mAcm -2, total deposition electric weight is 12Ccm -2, the make-and-break time ratio t of electric current Off/ t OnBe 5s: 1s, electrodeposition temperature is 30 ℃.In solution, feed argon gas in the electrodeposition process.Make the nanoscale platinum catalyst of high dispersive, high coverage rate, as shown in Figure 2.The pattern of Pt particle be diameter approximately from 20 to 100nm bulk, also have little ladder on the piece, specific area is very big.
The catalyst that above embodiment 1-3 is synthesized carries out the cyclic voltammetric test in methanol solution, test result is respectively as Fig. 3, Fig. 4, shown in Figure 5, and with do not have the segmentation electro-deposition, peak current density is constant to be 6mAcm -2, the deposition electric weight is 1.2Ccm -2, electric current make-and-break time ratio t Off/ t OnBe that 4s: 1s makes platinum catalyst (as shown in Figure 6) compare.As seen, do not compare with there being the segmentation electro-deposition, the platinum catalyst that adopts the segmentation electro-deposition to make has higher methanol oxidation peak-to-peak value current density, and methanol electro-oxidizing is had higher catalytic activity.
Embodiment 4:
Similar with embodiment 3 processes, but electrolyte is 0.5molL -1H 2SO 4+ 1.0mmolL -1H 2PtCl 6+ 10 -4MmolL -1LA.Pulse electrodeposition divides two stages to carry out pulse electrodeposition platinum, and the I stage is at peak current density 24mAcm -2Deposit 90s, the peak current density in II stage are 6mAcm -2, total deposition electric weight is 1.08Ccm -2, the make-and-break time ratio t of electric current Off/ t OnBe that 5s: 1s makes the nanoscale platinum catalyst of high dispersive, high coverage rate.
Embodiment 5:
Similar with embodiment 3 processes, but substrate is a carbon paper, and electrolyte is 0.5molL -1H 2SO 4+ 10mmolL -1H 2PtCl 6+ 10 -4MmolL -1PVP (molecular weight is 60000).Pulse electrodeposition divides two stages to carry out pulse electrodeposition platinum, and the I stage is at peak current density 24mAcm -2Deposit 120s, the peak current density in II stage are 4mAcm -2, total deposition electric weight is 2.4Ccm -2, the make-and-break time ratio t of electric current Off/ t OnBe that 5s: 1s makes the nanoscale platinum catalyst of high dispersive, high coverage rate.

Claims (5)

1, a kind of method of preparing platinum catalyst by electrodeposition is characterized in that, by working electrode, electrode, reference electrode are formed three-electrode system, at electrolyte for containing 0～10 -3The 0.5molL of mM additive -1H 2SO 4With 0.5～2mmolL -1H 2PtCl 6Mixed solution in divide two stages to carry out pulse electrodeposition platinum, adopt peak current density 12～36mAcm earlier -2, sedimentation time is 30～120s, thereafter, adopts peak current density 4～10mAcm -2, total deposition electric weight is 1～2.5Ccm -2, the make-and-break time ratio t of electric current Off/ t OnBe 1.5～6: 1, electrodeposition temperature is 20～60 ℃.
2, the method for claim 1 is characterized in that, described additive is 10 -5～10 -3MM is selected from a kind of in polyethylene glycol, lead acetate, polyvinylpyrrolidone, the citric acid.
3, the method for claim 1 is characterized in that, described working electrode be the ethanol that contains active carbon of configuration earlier with
Figure A20081010401800021
Mixed liquor adds 5～8 milligrams ratio according to every milliliter of ethanol, and the active carbon Vulcan XC-72 of acidified processing is placed ethanol, adds again The ultrasonic dispersion of solution (5wt.%) 30～60 minutes forms the carbon slurry; Pipette above-mentioned carbon slurry 150～300 μ L according to every square centimeter again and drip on the catalyst matrix surface, treat that ethanol evaporation is intact after, electrode in 50 ℃～70 ℃ vacuum drying 4～10h, is made employed working electrode in the electrodeposition process.
4, method as claimed in claim 3 is characterized in that,
Figure A20081010401800023
The mass percent of solution and alcohol suspension is 100: 1～100: 5.
5, method as claimed in claim 3 is characterized in that, described catalyst matrix is a kind of in glass carbon, graphite, carbon paper, the carbon cloth.
CN2008101040180A 2008-04-14 2008-04-14 Method for preparing platinum catalyst by electrodeposition Expired - Fee Related CN101259410B (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831666A (en) * 2010-05-28 2010-09-15 上海交通大学 Preparation method of nickel-based or titanium-based catalytic electrode for electrically catalyzing ammonia oxides
CN102780011A (en) * 2012-06-29 2012-11-14 青岛科技大学 Direct methanol fuel cell anode catalyst and preparation method of direct methanol fuel cell anode catalyst
CN102925939A (en) * 2012-11-26 2013-02-13 中国南方航空工业(集团)有限公司 Hard chromium electroplating method
CN103255457A (en) * 2013-04-28 2013-08-21 北京工业大学 Method for preparing nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition
CN107890866A (en) * 2017-12-13 2018-04-10 黑龙江科技大学 A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition
CN108832152A (en) * 2018-06-26 2018-11-16 李荣旭 A kind of band coating proton exchange membrane fuel cell metal flow-field plate
CN108950613A (en) * 2018-08-06 2018-12-07 首钢集团有限公司 A kind of preparation method of tin plate and the application of thus obtained tin plate
CN109100402A (en) * 2018-07-19 2018-12-28 深圳大学 A kind of monoatomic method of deposition platinum, compound and application
CN110350204A (en) * 2019-07-10 2019-10-18 广东工业大学 It is the fuel-cell catalyst and the preparation method and application thereof of shell by core, platinum of gold nano cluster
CN111841663A (en) * 2020-07-08 2020-10-30 中国工程物理研究院材料研究所 Electrochemical method for reducing size of carbon-supported metal nanoparticle electrocatalyst

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831666A (en) * 2010-05-28 2010-09-15 上海交通大学 Preparation method of nickel-based or titanium-based catalytic electrode for electrically catalyzing ammonia oxides
CN102780011A (en) * 2012-06-29 2012-11-14 青岛科技大学 Direct methanol fuel cell anode catalyst and preparation method of direct methanol fuel cell anode catalyst
CN102925939A (en) * 2012-11-26 2013-02-13 中国南方航空工业(集团)有限公司 Hard chromium electroplating method
CN102925939B (en) * 2012-11-26 2015-07-15 中国南方航空工业(集团)有限公司 Hard chromium electroplating method
CN103255457A (en) * 2013-04-28 2013-08-21 北京工业大学 Method for preparing nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition
CN103255457B (en) * 2013-04-28 2016-07-06 北京工业大学 A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium
CN107890866A (en) * 2017-12-13 2018-04-10 黑龙江科技大学 A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition
CN107890866B (en) * 2017-12-13 2020-07-31 黑龙江科技大学 Method for preparing platinum catalyst by electrodeposition with hydantoin derivative as complexing agent
CN108832152A (en) * 2018-06-26 2018-11-16 李荣旭 A kind of band coating proton exchange membrane fuel cell metal flow-field plate
CN108832152B (en) * 2018-06-26 2020-11-24 山东亚泰新材料科技有限公司 Coated metal flow field plate of proton exchange membrane fuel cell
CN109100402A (en) * 2018-07-19 2018-12-28 深圳大学 A kind of monoatomic method of deposition platinum, compound and application
CN109100402B (en) * 2018-07-19 2020-10-27 深圳大学 Method for depositing platinum monoatomic compound and application
CN108950613A (en) * 2018-08-06 2018-12-07 首钢集团有限公司 A kind of preparation method of tin plate and the application of thus obtained tin plate
CN110350204A (en) * 2019-07-10 2019-10-18 广东工业大学 It is the fuel-cell catalyst and the preparation method and application thereof of shell by core, platinum of gold nano cluster
CN111841663A (en) * 2020-07-08 2020-10-30 中国工程物理研究院材料研究所 Electrochemical method for reducing size of carbon-supported metal nanoparticle electrocatalyst

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