CN103022521A - Palladium-cobalt/graphene nano electro-catalyst and preparation method thereof - Google Patents

Palladium-cobalt/graphene nano electro-catalyst and preparation method thereof Download PDF

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Publication number
CN103022521A
CN103022521A CN2012105161439A CN201210516143A CN103022521A CN 103022521 A CN103022521 A CN 103022521A CN 2012105161439 A CN2012105161439 A CN 2012105161439A CN 201210516143 A CN201210516143 A CN 201210516143A CN 103022521 A CN103022521 A CN 103022521A
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palladium
cobalt
catalyst
graphene nano
preparation
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银凤翔
李国儒
陈标华
王亮
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention discloses a palladium-cobalt/graphene nano electro-catalyst and a preparation method thereof. According to the palladium-cobalt/graphene nano electro-catalyst, palladium serves as an active ingredient, cobalt serves as a cocatalyst, and graphene serves as a carrier; and in the catalyst, the mass fraction of the palladium is 10-40%, the mass fraction of the cobalt is 5-30%, and the balance is the carrier. According to the preparation method of the catalyst, graphite oxide nanosheets are ultrasonically dispersed into polylol, palladium salt liquid, cobalt salt liquid and sodium acetate liquid are then added and fully mixed uniformly, the mixture is then transferred into a microwave hydrothermal reaction kettle, and the filtering, washing and drying processes are carried out after reaction, thereby obtaining the palladium-cobalt/graphene nano electro-catalyst. The preparation method disclosed by the invention has the advantages of energy saving, high speed, simple process and the like; and the particle sizes of palladium and cobalt nanoparticles in the prepared palladium-cobalt/graphene nano electro-catalyst are uniform. The catalyst has high electro-catalytic activity to the electrooxidation of formic acid and is widely applied to fuel cells.

Description

A kind of palladium-cobalt/graphene nano electro-catalyst and preparation method thereof
Technical field
The present invention relates to a kind of eelctro-catalyst and preparation method thereof, particularly a kind of palladium-cobalt/graphene nano electro-catalyst and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells take hydrogen as fuel is considered to one of fuel cell technology of tool prospect, however since at present the extensive preparation of hydrogen and storage safe problem etc. do not solve so that Proton Exchange Membrane Fuel Cells is failed industrialization always.Direct methanol fuel cell can be avoided the preparation of hydrogen and storage safe problem, but methyl alcohol is difficult for catalytic oxidation and battery performance is descended.Studies show that recently with formic acid to be that the direct methanoic acid fuel cell of fuel has overcome above-mentioned these shortcomings to a certain extent, and formic acid almost there is not toxicity.Therefore, direct methanoic acid fuel cell is considered to a kind of very promising fuel cell system.
In the catalyst of direct methanoic acid fuel cell, Pt and Pd are the anode catalysts of most study, but Pt easily poisons because of CO absorption as the catalyst of formic acid catalytic oxidation, so that its catalytic activity reduces greatly.Studies show that recently, Pd has preferably formic acid catalytic oxidation activity and anti-CO poisoning performance.Studies show that simultaneously, usually in catalyst, add second or the third element, can further improve the performance of Pd catalyst, and add the Co co-catalyst in the catalyst and can obviously improve catalytic activity and the anti-CO poisoning performance of Pd, thereby make its anode catalyst as direct methanoic acid fuel cell have high activity and stable.
The preparation method traditional at the supported on carbon surface precious metal nano-particle catalyst mainly is based on dipping-reduction technique, but this method is difficult to the size of control load palladium metal particle on carbon carrier, and the dispersion of noble metal granule on carbon carrier neither be very even, especially for the Pt/C catalyst of preparation high capacity amount.Recently, polyxol method is proved to be to prepare a kind of effective ways of high dispersion metal nano particle.In this method, polyalcohol is as solvent and the reducing agent of slaine, and at high temperature polyalcohol makes the metal ion in the solution be reduced into metal nanoparticle.Microwave heating technique is owing to having fast, and evenly, energy-conservation and high efficiency advantage is used widely in the synthesizing of organic chemical synthesis and nano material recently.
Summary of the invention
The purpose of this invention is to provide a kind of palladium-cobalt/graphene nano electro-catalyst and preparation method thereof.
A kind of palladium-cobalt of the present invention/graphene nano electro-catalyst is take palladium as active component, and cobalt is co-catalyst, and Graphene is carrier; The mass fraction of palladium is 10~40% in the catalyst, and the mass fraction of cobalt is 5~30%, and surplus is carrier.
The preparation method of a kind of palladium-cobalt/graphene nano electro-catalyst mainly may further comprise the steps:
1) with in the ultrasonic ethylene glycol that is dispersed in liquid of graphite oxide nanometer sheet, then add palladium salting liquid, cobalt salt solution and SAS, fully mix, graphite oxide nanometer sheet content is 0.25~1.2g/L in the mixture, the concentration of palladium salt is 0.0005~0.05mol/L, the concentration of cobalt salt is 0.0001~0.01mol/L, and the concentration of sodium acetate is 0.05~0.1mol/L;
2) said mixture is transferred in the microwave hydrothermal reaction kettle, microwave heating reaction is after 5~10 minutes, after filtration, washing, oven dry, obtains palladium-cobalt/graphene nano electro-catalyst.
Among the present invention, described palladium salt is palladium bichloride or palladium.
Compared with the prior art, the present invention adopts polyalcohol method and microwave technology, Pd nano particle has tiny and uniform particle diameter in the catalyst that is synthesized, and average grain diameter can be regulated and control about 3.0nm, and Pd nano particle high degree of dispersion on graphene nanometer sheet is even; In the catalyst preparation, add the co-catalyst cobalt chloride, can obviously improve the catalytic activity of platinum selective oxidation CO, reduced reaction temperature, also reduced the content of noble metal platinum simultaneously; The preparation method has fast, evenly, and the energy-conservation and high advantage of efficient.
Embodiment
EXAMPLE l:
The ultrasonic processing of 200mg graphite oxide nanometer sheet is dispersed in the ethylene glycol of 400mL, then adds the palladium chloride solution of 20mL 0.04M, the cobalt chloride solution of 10mL 0.1M and the SAS of 20mL 1M, and fully mix.Should transfer in the microwave hydrothermal reaction kettle by uniform mixture carry out microwave radiation heating reaction 10min.After the cooling, after filtration, with acetone and deionized water fully wash, 90 ℃ of oven dry, obtain palladium-cobalt/graphene nano electro-catalyst.As a comparison, synthesize in the same way palladium/graphene catalyst (mass fraction of palladium is 24.6%).
To Oxidation of Formic Acid electrocatalysis characteristic test and relatively: a small amount of eelctro-catalyst (palladium-cobalt/Graphene, palladium/graphene nano electro-catalyst) and an amount of 5% Nafion solution and absolute ethyl alcohol are mixed under ul-trasonic irradiation, should be coated on the glassy carbon electrode by uniform mixture, rear as measuring work electrode 80 ℃ of lower oven dry.Reference electrode is saturated calomel electrode (SCE) during measurement, and electrolyte is lM CHOOH+lMHClO 4, platinized platinum is to electrode.Estimate nanometer electrical catalyst to the electro catalytic activity of formic acid electrochemical oxidation with cyclic voltammetry, sweep speed is 20mV/s.On the Pd-Co/ Graphene that records in above-mentioned preparation, the Pd/ graphene nano electro-catalyst, the peak current of formic acid electroxidation is respectively 18.3mA and 10.7mA, shows that Pd-Co/ Graphene eelctro-catalyst has the higher electro catalytic activity to Oxidation of Formic Acid than Pd/ graphen catalyst.
Embodiment 2
The ultrasonic processing of 600mg graphite oxide nanometer sheet is dispersed in the ethylene glycol of 500mL, then adds the palladium chloride solution of 28mL 0.1M, the cobalt chloride solution of 15mL 0.1M and the SAS of 25mL 1M, and fully mix.Should transfer in the microwave hydrothermal reaction kettle by uniform mixture carry out microwave radiation heating reaction 8min.After the cooling, after filtration, with acetone and deionized water fully wash, 90 ℃ of oven dry, obtain palladium-cobalt/graphene nano electro-catalyst.As a comparison, synthesize in the same way palladium/graphene catalyst (mass fraction of palladium is 30%).
The method test of pressing embodiment 1 relatively Pd-Co/ Graphene and Pd/ graphen catalyst to the catalytic performance of formic acid electroxidation.The peak current of formic acid electroxidation is respectively 25.6mA and 15.3mA on the Pd-Co/ Graphene that records under the same terms in above-mentioned preparation and the Pd/ graphen catalyst, illustrates that Pd-Co/ Graphene eelctro-catalyst has the higher electro catalytic activity to Oxidation of Formic Acid than Pd/ graphen catalyst.
Example 3
The ultrasonic processing of 400mg graphite oxide nanometer sheet is dispersed in the ethylene glycol of 600mL, then adds the palladium chloride solution of 20mL 0.05M, the cobalt chloride solution of 20mL 0.1M and the SAS of 30mL 1M, and fully mix.Should transfer in the microwave hydrothermal reaction kettle by uniform mixture carry out microwave radiation heating reaction 6min.After the cooling, after filtration, with acetone and deionized water fully wash, 90 ℃ of oven dry, obtain palladium-cobalt/graphene nano electro-catalyst.As a comparison, synthesize in the same way palladium/graphene catalyst (mass fraction of palladium is 17%).
The method test of pressing embodiment 1 relatively Pd/ Graphene and palladium/graphene catalyst to the catalytic performance of formic acid electroxidation.The peak current of formic acid electroxidation is respectively 9.2mA and 5.3mA on the Pd/ Graphene that records under the same terms in above-mentioned preparation and the palladium/graphene catalyst, illustrates that Pd-Co/ Graphene eelctro-catalyst has the higher electro catalytic activity to Oxidation of Formic Acid than Pd/ Graphene eelctro-catalyst.

Claims (4)

1. palladium-cobalt/graphene nano electro-catalyst comprises active component palladium and carrier Graphene, it is characterized in that this catalyst is take cobalt as the group catalyst; The mass fraction of palladium is 10~40% in the catalyst, and the mass fraction of cobalt is 5~30%, and surplus is carrier.
2. the method for preparing palladium-cobalt claimed in claim 1/graphene nano electro-catalyst is characterized in that preparation process is as follows:
1) is dispersed in the ethylene glycol the graphite oxide nanometer sheet is ultrasonic, then add palladium salting liquid, cobalt salt solution and SAS, fully mix, graphite oxide nanometer sheet content is 0.25~1.2g/L in the mixture, the concentration of palladium salt is 0.0005~0.05mol/L, the concentration of cobalt salt is 0.0001~0.01mol/L, and the concentration of sodium acetate is 0.05~0.1mol/L;
2) said mixture is transferred in the microwave hydrothermal reaction kettle, microwave heating reaction is after 5~10 minutes, after filtration, washing, oven dry, obtains palladium/graphene nano electro-catalyst.
3. the preparation method of a kind of palladium-cobalt according to claim 2/graphene nano electro-catalyst is characterized in that described palladium salt is palladium bichloride or palladium.
4. the preparation method of a kind of palladium-cobalt according to claim 2/graphene nano electro-catalyst is characterized in that described cobalt salt is cobalt chloride, cobalt nitrate, cobalt carbonate or cobalt acetate.
CN2012105161439A 2012-12-05 2012-12-05 Palladium-cobalt/graphene nano electro-catalyst and preparation method thereof Pending CN103022521A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104307512A (en) * 2014-10-14 2015-01-28 武汉大学苏州研究院 Supported palladium catalyst and preparation method and application thereof
CN104549366A (en) * 2015-01-20 2015-04-29 西南大学 Preparation method of gold-palladium-cobalt alloy/carbon high-performance ethanol oxidation catalyst
CN104588035A (en) * 2015-01-20 2015-05-06 西南大学 Preparation method for gold-palladium-cobalt core-shell structure (Au@PdCo)/carbon high-performance ethanol oxidation catalyst
CN106129423A (en) * 2016-06-27 2016-11-16 西南大学 A kind of Graphene supports preparation method of Pd nano flower catalyst and products thereof and the application in aminic acid fuel battery
CN106810419A (en) * 2015-11-30 2017-06-09 山东华鲁恒升化工股份有限公司 For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof
CN107051562A (en) * 2016-12-28 2017-08-18 中南大学 A kind of preparation method of graphene-based carbonic acid Co catalysts for cyclohexene oxide
CN107104237A (en) * 2017-04-26 2017-08-29 江苏大学 The preparation method and application of coralliform PdCo bianry alloy catalyst
CN108155392A (en) * 2017-11-30 2018-06-12 昆明理工大学 A kind of preparation method of redox graphene load Pd-M nano-composite catalysts
CN108490061A (en) * 2018-03-19 2018-09-04 广东华晟安全职业评价有限公司 A kind of detection method of detection hydrogen cyanide and cyanide content
CN110183679A (en) * 2019-06-25 2019-08-30 淮阴师范学院 A kind of accessory of metal organic frame and preparation
CN112531178A (en) * 2020-11-23 2021-03-19 上海纳米技术及应用国家工程研究中心有限公司 Fuel cell cathode multi-metal doped multi-element non-metal oxygen reduction catalyst and preparation method thereof
CN113634255A (en) * 2021-08-24 2021-11-12 武汉理工大学 Loaded Co3O4Preparation method of granular nano carbon composite catalytic material

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CN101151745A (en) * 2005-02-10 2008-03-26 布鲁克哈文科学协会 Palladium-cobalt particles as oxygen-reduction electrocatalysts
CN101740786A (en) * 2009-12-14 2010-06-16 浙江大学 PtRu/graphene nano electro-catalyst and preparation method thereof
CN101740785A (en) * 2009-12-14 2010-06-16 浙江大学 Palladium/graphene nano electro-catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101151745A (en) * 2005-02-10 2008-03-26 布鲁克哈文科学协会 Palladium-cobalt particles as oxygen-reduction electrocatalysts
CN101740786A (en) * 2009-12-14 2010-06-16 浙江大学 PtRu/graphene nano electro-catalyst and preparation method thereof
CN101740785A (en) * 2009-12-14 2010-06-16 浙江大学 Palladium/graphene nano electro-catalyst and preparation method thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104307512A (en) * 2014-10-14 2015-01-28 武汉大学苏州研究院 Supported palladium catalyst and preparation method and application thereof
CN104549366A (en) * 2015-01-20 2015-04-29 西南大学 Preparation method of gold-palladium-cobalt alloy/carbon high-performance ethanol oxidation catalyst
CN104588035A (en) * 2015-01-20 2015-05-06 西南大学 Preparation method for gold-palladium-cobalt core-shell structure (Au@PdCo)/carbon high-performance ethanol oxidation catalyst
CN106810419A (en) * 2015-11-30 2017-06-09 山东华鲁恒升化工股份有限公司 For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof
CN106810419B (en) * 2015-11-30 2020-10-20 山东华鲁恒升化工股份有限公司 Graphene-loaded metal compound for preparing ethanol catalyst by acetic acid hydrogenation and preparation method thereof
CN106129423A (en) * 2016-06-27 2016-11-16 西南大学 A kind of Graphene supports preparation method of Pd nano flower catalyst and products thereof and the application in aminic acid fuel battery
CN106129423B (en) * 2016-06-27 2018-07-27 西南大学 Preparation method of a kind of graphene support Pd nano flower catalyst and products thereof and the application in aminic acid fuel battery
CN107051562B (en) * 2016-12-28 2019-07-16 中南大学 A kind of preparation method of the graphene-based carbonic acid Co catalysts for cyclohexene oxide
CN107051562A (en) * 2016-12-28 2017-08-18 中南大学 A kind of preparation method of graphene-based carbonic acid Co catalysts for cyclohexene oxide
CN107104237A (en) * 2017-04-26 2017-08-29 江苏大学 The preparation method and application of coralliform PdCo bianry alloy catalyst
CN108155392A (en) * 2017-11-30 2018-06-12 昆明理工大学 A kind of preparation method of redox graphene load Pd-M nano-composite catalysts
CN108490061A (en) * 2018-03-19 2018-09-04 广东华晟安全职业评价有限公司 A kind of detection method of detection hydrogen cyanide and cyanide content
CN110183679A (en) * 2019-06-25 2019-08-30 淮阴师范学院 A kind of accessory of metal organic frame and preparation
CN112531178A (en) * 2020-11-23 2021-03-19 上海纳米技术及应用国家工程研究中心有限公司 Fuel cell cathode multi-metal doped multi-element non-metal oxygen reduction catalyst and preparation method thereof
CN113634255A (en) * 2021-08-24 2021-11-12 武汉理工大学 Loaded Co3O4Preparation method of granular nano carbon composite catalytic material

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Application publication date: 20130403