CN100349656C - Carbon loaded hollow cobalt platinum nanometer particle electrocatalyst and its preparation method - Google Patents
Carbon loaded hollow cobalt platinum nanometer particle electrocatalyst and its preparation method Download PDFInfo
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- CN100349656C CN100349656C CNB2006100501710A CN200610050171A CN100349656C CN 100349656 C CN100349656 C CN 100349656C CN B2006100501710 A CNB2006100501710 A CN B2006100501710A CN 200610050171 A CN200610050171 A CN 200610050171A CN 100349656 C CN100349656 C CN 100349656C
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 title claims abstract description 33
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GUBSQCSIIDQXLB-UHFFFAOYSA-N cobalt platinum Chemical compound [Co].[Pt].[Pt].[Pt] GUBSQCSIIDQXLB-UHFFFAOYSA-N 0.000 title abstract 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 150000003057 platinum Chemical class 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000002105 nanoparticle Substances 0.000 claims description 37
- AVMBSRQXOWNFTR-UHFFFAOYSA-N cobalt platinum Chemical compound [Pt][Co][Pt] AVMBSRQXOWNFTR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical group [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 4
- 239000012266 salt solution Substances 0.000 abstract 4
- 239000000243 solution Substances 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 238000000034 method Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229910020707 Co—Pt Inorganic materials 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000006056 electrooxidation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 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 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
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Abstract
The present invention discloses a carbon carried hollow cobalt-platinum nanometer particle electrocatalyst. The electrocatalyst is characterized in that each nanometer particle carried by each carbon carrier has a hollow structure, an inner layer of the hollow structure is prepared from metallic cobalt, and a surface layer of the hollow structure is prepared from metallic platinum. Preparation steps comprise: 1) cobalt salt is dissolved in deionized water, a stabilizing agent is added to a cobalt salt solution, nitrogen is led into the cobalt salt solution for removing oxygen in the solution; 2) a sodium borohydride solution is dripped into the cobalt salt solution under the shield of nitrogen to react for 30 to 50 minutes for reducing cobalt ions in a mixed solution into metallic nanometer particles, and platinum salt solution is dripped into the mixed solution to react for 30 to 60 minutes; 3) nanometer carbon carriers are added to the mixed solution and stirred for 1 to 2 hours, and then, a final mixed solution is filtered, cleaned and dried to obatin the hollow cobalt-platinum/carbon nanometer electrocatalyst. The carbon carried hollow cobalt-platinum nanometer particle electrocatalyst not only can enhance the utilization rate of the noble metal platinum, but also has better electrocatalysis property as compared with a common solid core Pt/C electrocatalyst. The electrocatalyst has wide application in fuel cells.
Description
Technical field
The present invention relates to eelctro-catalyst in the fuel cell and preparation method thereof, especially relate to carbon load hollow cobalt platinum nanometer particle electrocatalyst and preparation method thereof.
Background technology
Carbon load platinum and platinum alloy nano particle are with its excellent catalytic performance, and as catalyst, the eelctro-catalyst in the battery that especially acts as a fuel has obtained using widely.But act as a fuel the battery eelctro-catalyst, the catalytic performance of metal platinum nano-particle and its particle diameter, carrying capacity, dispersiveness and surface area etc. have confidential relation.The price of platinum costliness also makes its practical application be subjected to certain restriction on the other hand.Therefore, people are usually by particle diameter that reduces platinum particles and the electrocatalysis characteristic that metal platinum particle high degree of dispersion is improved the metal platinum particle on carbon carrier.
The nano platinum particle of using as eelctro-catalyst generally need load on certain carrier, and material with carbon element is the most frequently used carrier.Some special carbon carrier surfaces have a large amount of functional groups, have certain interaction with the noble metal nano particles of area load, can improve the electrocatalysis characteristic and the stability of catalytic performance of noble metal nano particles.Simultaneously, the high degree of dispersion of platinum nanoparticles on carbon carrier can improve the utilization rate of nano platinum particle, saves the consumption of noble metal platinum greatly.XC-72 nano-sized carbon and CNT have high specific surface, and the carrier that can be used as eelctro-catalyst usually uses.Studies have shown that XC-72 nano-sized carbon and carbon nanotube loaded platinum and platinum alloy nano particle have good catalytic action as eelctro-catalyst.But these platinum and platinum alloy nano particle are solid nano particles, make that the utilization rate of noble metal platinum is not very high.
Recently the metal Nano structure of hollow is with high specific area, lower density, low cost and save advantage such as material and make its and corresponding non-hollow metal nano material that different physical and chemical performances be arranged, so caused people's extensive concern.At present, this hollow metal nanometer particle process method mainly is based on a kind of template method.Template commonly used has meso-porous alumina, polyethylene Nano microsphere, silicon ball and vesica etc.This method at first is that metal is restored on these templates, and then by the method for some heating or dissolving template is removed, and has just obtained the metal Nano structure of hollow at last.Sun etc. have proposed a kind of method (Metal nanostructures with hollow interio Adv.Mater. of synthetic hollow noble metal nano structure, 2003,15:7-8), the cardinal principle of this method is based on intermetallic displacement reaction, at first in solution, synthesize comparatively active argent nano particle with chemical reduction method, the salt precursor thing that adds Precious Metals-Gold, platinum or palladium then refluxes under 100 ℃ condition and has obtained the hollow nanostructures may of gold, platinum or palladium at last.On the other hand, if the internal layer of the inside is more cheap metal (as metallic cobalt) in the hollow nano particle, the top layer of outside is the noble metal (as platinum) with electrocatalysis characteristic, and the cobalt platinum nanometer particle of this hollow will have excellent electrocatalysis characteristic.But, up to the present also do not find the report of the cobalt platinum nanometer particle electrocatalyst of carbon load hollow.
Summary of the invention
The purpose of this invention is to provide a kind of carbon load hollow cobalt platinum nanometer particle electrocatalyst and preparation method thereof with excellent electrocatalysis characteristic.
The cobalt platinum nanometer particle electrocatalyst of the carbon load hollow of invention, the nano particle that loads on the carbon carrier is a hollow structure, the internal layer of hollow structure is a metallic cobalt, extexine is a metal platinum, the mass percent of platinum is 10～20% in the catalyst, the mass percent of cobalt is 3～17%, and all the other are carbon.
The preparation method of carbon load hollow cobalt platinum nanometer particle electrocatalyst, its step is as follows:
1) cobalt salt is dissolved in the deionized water, compound concentration is the 0.002-0.006mol/L cobalt saline solution, adds an amount of stabilizing agent, and making the concentration of stabilizing agent in cobalt saline solution is 0.002-0.006mol/L, and feeding nitrogen is removed the oxygen in the solution;
2) under nitrogen protection, the solution that dropwise adds sodium borohydride, the mol ratio of sodium borohydride and cobalt salt is 1: 1～1: 1.1, react and made the cobalt ions in the solution be reduced to metal nanoparticle in 30～50 minutes, dropwise adding concentration again is the platinum salting liquid of 0.001-0.01mol/L, the mol ratio of platinum salt and cobalt salt is 1: 4～1: 6, continues stirring reaction 30～60 minutes;
3) add the nano-sized carbon carrier and stirred 1～2 hour, after filtration, washing, oven dry, obtain the cobalt platinum nanometer particle electrocatalyst of carbon load hollow.
Among the present invention, said platinum salt is potassium chloroplatinate.Said cobalt salt is cobalt chloride or cobaltous sulfate.Said nano-sized carbon carrier is XC-72 nano-sized carbon or CNT.Said stabilizing agent is natrium citricum or polyvinylpyrrolidone.
The present invention has following beneficial effect compared with the prior art:
Carbon load hollow cobalt platinum nanometer particle electrocatalyst of the present invention, the nano particle that loads on the carbon carrier is a hollow structure, the internal layer of hollow structure is a metallic cobalt, and extexine is the noble metal platinum with electrocatalysis characteristic, therefore can improve the utilization rate and the electrocatalysis characteristic thereof of noble metal platinum.The synthetic hollow Co-Pt/C eelctro-catalyst of the inventive method has better electrocatalysis characteristic than general solid Pt/C eelctro-catalyst, has in fuel cell widely and uses.
The specific embodiment
Embodiment 1:
100 milliliters of 0.002mol/L cobalt chloride solutions join in 250 milliliters the three-neck flask, add natrium citricum then, and natrium citricum concentration in synthetic solvent is 0.002mol/L.Constantly stir with magnetic stirring apparatus, and feed nitrogen after 15 minutes in synthetic solvent, dropwise add the 11mL sodium borohydride solution, concentration is 0.02mol/L, keeps feeding nitrogen in the course of reaction.Behind the question response 40 minutes, 0 milliliter of 0.001mol/L platinum acid chloride solution of Dropwise 5 in synthetic solvent again, after the magnetic agitation 30 minutes, add 37 milligrams of XC-72 nano-sized carbon again, the logical nitrogen of continuation also stirs after 1 hour the mixture in the flask is fully washed with acetone and deionized water through filtering the back, 90 ℃ of oven dry, obtain the Co-Pt/XC-72 eelctro-catalyst (mass fraction of platinum is 20%, and the mass fraction of cobalt is 6%) of hollow.Transmission electron microscope observing shows that the nano particle in the catalyst is the nano particle of hollow, and is evenly distributed on the XC-72 nano-sized carbon carrier, and its average diameter is about 23nm, about the thickness 3nm of shell.
As a comparison, directly with the method for sodium borohydride as reducing agent reduction chloroplatinic acid, synthetic general Pt/XC-72 nanometer electrical catalyst (mass fraction of platinum is 20%).Transmission electron microscope observing shows that nano platinum particle is not the nano particle of hollow in the catalyst, and its average grain diameter is 4.8nm.
Electrocatalysis characteristic test is relatively: a spot of catalyst and an amount of 5% Nafion solution and deionized water are mixed under the ultrasonic wave effect, should be coated on the glassy carbon electrode by uniform mixture, 80 ℃ dry down after as measuring working electrode.Reference electrode is saturated calomel electrode (SCE) during electrochemical measurement, and platinized platinum is to electrode, and electrolyte is 2M CH
3OH+1M H
2SO
4, 30 ℃ of temperature.Compare the electro catalytic activity of catalyst with cyclic voltammetry to methanol electrooxidation.
The peak current of methanol electro-oxidizing is 11.2mA on the Co-Pt/XC-72 eelctro-catalyst that records under the same conditions in hollow; The peak current of methanol electro-oxidizing is 5.3mA on general Pt/XC-72 nanometer electrical catalyst.Illustrate that the former has more high electrocatalytic active than the latter to the electrochemical oxidation of methyl alcohol.
Embodiment 2:
100 milliliters of 0.006mol/L cobalt chloride solutions join in 250 milliliters the three-neck flask, add natrium citricum then, and natrium citricum concentration in synthetic solvent is 0.006mol/L.Constantly stir with magnetic stirring apparatus, and feed nitrogen in synthetic solvent, after 20 minutes, dropwise add the 32mL sodium borohydride solution, concentration is 0.02mol/L, keeps feeding nitrogen in the course of reaction.Behind the question response 50 minutes, in synthetic solvent, drip 10 milliliters of 0.01mol/L potassium chloroplatinate solution again, after the magnetic agitation 40 minutes, add 62 milligrams of XC-72 nano-sized carbon again, the logical nitrogen of continuation also stirs after 2 hours the mixture in the flask is fully washed with acetone and deionized water through filtering the back, 90 ℃ of oven dry, obtain the Co-Pt/XC-72 eelctro-catalyst (mass fraction of platinum is 20%, and the mass fraction of cobalt is 17%) of hollow.Transmission electron microscope observing shows that nano particle is the nano particle of hollow in the catalyst, and is evenly distributed on the XC-72 nano-sized carbon carrier, and its average diameter is about 25nm, about the thickness 4nm of shell.
As a comparison, directly with the method for sodium borohydride as reducing agent reduction potassium chloroplatinate, synthetic general Pt/XC-72 nanometer electrical catalyst (mass fraction of platinum is 20%).Transmission electron microscope observing shows that nano platinum particle is not the nano particle of hollow in the catalyst, and its average grain diameter is 4.8nm.
Carry out the electrocatalysis characteristic test relatively by the method for embodiment 1.
The peak current of methanol electro-oxidizing is 10.2mA on the Co-Pt/XC-72 eelctro-catalyst that records under the same conditions in hollow; The peak current of methanol electro-oxidizing is 5.2mA on general Pt/XC-72 nanometer electrical catalyst.Illustrate that the former has more high electrocatalytic active than the latter to the electrochemical oxidation of methyl alcohol.
Embodiment 3:
100 milliliters of 0.004mol/L cobalt sulfate solutions join in 250 milliliters the three-neck flask, add natrium citricum then, and natrium citricum concentration in synthetic solvent is 0.004mol/L.Constantly stir with magnetic stirring apparatus, and feed nitrogen in synthetic solvent, after 15 minutes, dropwise add the 20mL sodium borohydride solution, concentration is 0.02mol/L, keeps feeding nitrogen in the course of reaction.Behind the question response 40 minutes, in synthetic solvent, drip 25 milliliters of 0.004mol/L platinum acid chloride solutions again, after the magnetic agitation 30 minutes, add 74 milligrams of CNTs again, the logical nitrogen of continuation also stirs after 1 hour the mixture in the flask is fully washed with acetone and deionized water through filtering the back, and 90 ℃ of oven dry, (mass fraction of platinum is 20% to obtain hollow Pt/CNTs eelctro-catalyst, the mass fraction of cobalt is 6%).Transmission electron microscope observing shows that nano particle is the nano particle of hollow in the catalyst, and is evenly distributed on the CNT, and its average diameter is about 24nm, about the thickness 2.7nm of shell.
As a comparison, directly with the method for sodium borohydride as reducing agent reduction chloroplatinic acid, synthetic general Pt/CNTs nanometer electrical catalyst (mass fraction of platinum is 20%).Transmission electron microscope observing shows that nano platinum particle is not the nano particle of hollow in the catalyst, and its average grain diameter is 4.5nm.
Carry out the electrocatalysis characteristic test relatively by the method for embodiment 1.
The peak current of methanol electro-oxidizing is 11.3mA on the Co-Pt/CNTs eelctro-catalyst that records under the same conditions in hollow; The peak current of methanol electro-oxidizing is 6.5mA on general Pt/CNTs eelctro-catalyst.Illustrate that the former has more high electrocatalytic active than the latter to the electrochemical oxidation of methyl alcohol.
Embodiment 4:
100 milliliters of 0.0025mol/L cobalt chloride solutions join in 250 milliliters the three-neck flask, add polyvinylpyrrolidone then, and polyvinylpyrrolidone concentration in synthetic solvent is 0.0025mol/L.Constantly stir with magnetic stirring apparatus, and feed nitrogen in synthetic solvent, after 15 minutes, dropwise add the 13ml sodium borohydride solution, concentration is 0.02mol/L, keeps feeding nitrogen in the course of reaction.Behind the question response 35 minutes, in synthetic solvent, drip 25 milliliters of 0.002mol/L platinum acid chloride solutions again, after the magnetic agitation 30 minutes, add 84 milligrams of XC-72 nano-sized carbon again, the logical nitrogen of continuation also stirs after 1 hour the mixture in the flask is fully washed with acetone and deionized water through filtering the back, 90 ℃ of oven dry, obtain the Co-Pt/XC-72 eelctro-catalyst (mass fraction of platinum is 10%, and the mass fraction of cobalt is 6%) of hollow.Transmission electron microscope observing shows that nano particle is the nano particle of hollow in the catalyst, and is evenly distributed on the XC-72 nano-sized carbon carrier, and its average diameter is about 22nm, about the thickness 2.6nm of shell.
As a comparison, directly with the method for sodium borohydride as reducing agent reduction chloroplatinic acid, synthetic general Pt/XC-72 nanometer electrical catalyst (mass fraction of platinum is 10%).Transmission electron microscope observing shows that nano platinum particle is not the nano particle of hollow in the catalyst, and its average grain diameter is 4.5nm.
Carry out the electrocatalysis characteristic test relatively by the method for embodiment 1.The peak current that records methanol electro-oxidizing on hollow Co-Pt/XC-72 eelctro-catalyst under the same conditions is 6.5mA; The peak current of methanol electro-oxidizing is 3.4mA on general Pt/XC-72 nanometer electrical catalyst.Illustrate that the former has more high electrocatalytic active than the latter to the electrochemical oxidation of methyl alcohol.
Claims (6)
1. the cobalt platinum nanometer particle electrocatalyst of a carbon load hollow, the nano particle that it is characterized in that loading on the carbon carrier is a hollow structure, the internal layer of hollow structure is a metallic cobalt, extexine is a metal platinum, the mass percent of platinum is 10～20% in the catalyst, the mass percent of cobalt is 3～17%, and all the other are carbon.
2. the preparation method of the cobalt platinum nanometer particle electrocatalyst of carbon load hollow according to claim 1 is characterized in that step is as follows:
1) cobalt salt is dissolved in the deionized water, compound concentration is the 0.002-0.006mol/L cobalt saline solution, adds an amount of stabilizing agent, and making the concentration of stabilizing agent in cobalt saline solution is 0.002-0.006mol/L, and feeding nitrogen is removed the oxygen in the solution;
2) under nitrogen protection, the solution that dropwise adds sodium borohydride, the mol ratio of sodium borohydride and cobalt salt is 1: 1～1: 1.1, react and made the cobalt ions in the solution be reduced to metal nanoparticle in 30～50 minutes, dropwise adding concentration again is the platinum salting liquid of 0.001-0.01mol/L, the mol ratio of platinum salt and cobalt salt is 1: 4～1: 6, continues stirring reaction 30～60 minutes;
3) add the nano-sized carbon carrier and stirred 1-2 hour, after filtration, washing, oven dry, obtain the cobalt platinum nanometer particle electrocatalyst of carbon load hollow.
3. the preparation method of the cobalt platinum nanometer particle electrocatalyst of carbon load hollow according to claim 2 is characterized in that said platinum salt is potassium chloroplatinate.
4. the preparation method of the cobalt platinum nanometer particle electrocatalyst of carbon load hollow according to claim 2 is characterized in that said cobalt salt is: cobalt chloride or cobaltous sulfate.
5. the preparation method of the cobalt platinum nanometer particle electrocatalyst of carbon load hollow according to claim 2 is characterized in that said nano-sized carbon carrier is XC-72 nano-sized carbon or CNT.
6. the preparation method of the cobalt platinum nanometer particle electrocatalyst of carbon load hollow according to claim 2 is characterized in that said stabilizing agent is natrium citricum or polyvinylpyrrolidone.
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| CN103063832A (en) * | 2013-01-05 | 2013-04-24 | 福州大学 | Immunoassay method based on platinum nanoparticle mimic enzyme |
| CN104971737B (en) * | 2014-04-09 | 2017-12-01 | 中国科学院大连化学物理研究所 | A kind of PtCo nano-hollow balls, its preparation method and application |
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