CN100346876C - Electrocatalyst with hollow nanometer platinum ruthenium alloy particle supported on carbon surface and its preparing method - Google Patents
Electrocatalyst with hollow nanometer platinum ruthenium alloy particle supported on carbon surface and its preparing method Download PDFInfo
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- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910000929 Ru alloy Inorganic materials 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 18
- 239000010411 electrocatalyst Substances 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 150000003057 platinum Chemical class 0.000 claims abstract description 9
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 9
- 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
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 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
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 239000002082 metal nanoparticle Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 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
- 238000011068 loading method Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052697 platinum Inorganic materials 0.000 abstract description 9
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000007513 acids Chemical class 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 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
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000010287 polarization Effects 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
- 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
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Abstract
The present invention discloses an electrocatalyst with hollow nanometer platinum ruthenium alloy particles supported on the surface of carbon. The nanometer platinum ruthenium alloy particles are in a hollow structure, and the atomic ratio of alloy composition is Pt<x>Ru<y>, wherein X is from 0.2 to 0.8, Y is from 0.8 to 0.2, and X plus Y is 1. The mass percent of the nanometer platinum ruthenium alloy particles accounts for 9% to 30% of the catalyst is from, and the rest component is balance of carbon. A preparing method of the catalyst comprises the following steps: 1) dissolving cobalt salt in deionized water, adding a stabilizing agent, and introducing nitrogen to remove oxygen in the solution; 2) under the protection of nitrogen, adding a sodium borohydride solution to deoxidize cobalt ions into nanometer metal particles, and adding a mixed solution of platinum salt and ruthenium salt for continuous reaction; 3) adding the carbon carrier, stirring for 1 to 2 hours, filtering, washing and drying to attain the hollow platinum ruthenium/carbon electrocatalyst. The catalyst can increase the utilization ratio of platinum and ruthenium, and has excellent electrocatalytic performance on the electrooxidation of methanol; thus, the catalyst can be widely used in fuel batteries.
Description
Technical field
The present invention relates to eelctro-catalyst in the fuel cell and preparation method thereof, especially relate to carbon load hollow nanometer platinum ruthenium alloy particle eelctro-catalyst and preparation method thereof.
Background technology
Carbon material supported nanometer platinum ruthenium alloy particle has very important application at fuel cell, the platinum-ruthenium alloys catalyst has excellent anti-carbon monoxide poisoning performance than monometallic platinum, therefore is used as the important electro catalytic electrode material of DMFC and the fuel cell that uses the hydrogen that contains micro CO.XC-72 nano-sized carbon and CNT have high specific surface, have obtained using widely as catalyst carrier.XC-72 nano-sized carbon and carbon nanotube loaded platinum-ruthenium alloys have good catalytic action to methyl alcohol.But the price of the costliness of platinum and ruthenium makes its practical application be subjected to certain restriction.
Because the metal nanoparticle of hollow structure not only has specific area height, characteristics that density is lower, and compare with non-hollow metal nano material new physical and chemical performance is arranged, the use amount that the noble metal nano particles of while hollow structure can be saved noble metal, the cost of reduction material.Therefore, the synthetic and application study of the metal nanoparticle of hollow structure has caused people's very big interest recently.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 gold nano structure of hollow at last.Sun etc. have proposed a kind of method (Metal nanostructureswith hollow interior of synthetic hollow noble metal nano structure, Adv.Mater., 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.But, up to the present also do not find the report of the nanometer platinum ruthenium alloy particle eelctro-catalyst of carbon load hollow.
Summary of the invention
The purpose of this invention is to provide a kind of supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst and preparation method thereof with excellent electrocatalysis characteristic and raising noble metal utilization rate.
The supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst of invention, the platinum irmn alloy nano particle that it is characterized in that loading on carbon surface is a hollow structure, the atomic ratio that platinum-ruthenium alloys is formed is expressed as Pt
xRu
y, X=0.2～0.8 wherein, Y=0.8～0.2, X+Y=1, the mass fraction of nanometer platinum ruthenium alloy particle is 9%～30% in the catalyst, all the other are carbon.
The preparation method of supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst, 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, and then dropwise add the mixed solution of platinum salt and ruthenium salt, continued stirring reaction 30～60 minutes, the concentration of platinum salt is 0.002～0.05mol/L in the mixed solution, the concentration of ruthenium salt is 0.0005～0.05mol/L, and the ratio of platinum salt and ruthenium salt amount sum and cobalt salt amount is 1: 2～1: 3;
3) add carbon carrier and stirred 1～2 hour, after filtration, washing, oven dry, obtain at supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst.
Among the present invention, said platinum salt is chloroplatinic acid or potassium chloroplatinate; Ruthenium salt is ruthenic chloride; Said cobalt salt is cobalt chloride or cobaltous sulfate; Said carbon carrier is XC-72 nano-sized carbon or CNT; Stabilizing agent is natrium citricum or polyvinylpyrrolidone.
The present invention has following beneficial effect compared with the prior art:
Carbon load hollow nanometer platinum ruthenium alloy particle eelctro-catalyst of the present invention, the nanometer platinum ruthenium alloy particle that loads on carbon surface is a hollow structure, therefore can improve the utilization rate of noble metal platinum and ruthenium, helps saving noble metal platinum and ruthenium.The eelctro-catalyst that the inventive method is synthesized has excellent electrocatalysis characteristic to the electrochemical oxidation of methyl alcohol, has in fuel cell widely and uses.
The specific embodiment
Embodiment 1:
68 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 adding concentration is the sodium borohydride solution 14mL of 0.01mol/L, and reaction is 30 minutes under logical nitrogen protection; Drip the mixed solution of 20 milliliters of potassium chloroplatinates and ruthenic chloride then in synthetic solvent, the concentration of potassium chloroplatinate is 0.002mol/L in the mixed solution, and the concentration of ruthenic chloride is 0.0005mol/L, continues magnetic agitation reaction 30 minutes; Add 90 milligrams of XC-72 nano-sized carbon at last again, continue to lead to nitrogen and stir after 1 hour the mixture in the flask is fully washed with deionized water after filtering,, obtain the platinum ruthenium/XC-72 eelctro-catalyst of hollow 90 ℃ of oven dry.The mass fraction of platinum-ruthenium alloys is 9% in the catalyst, platinum-ruthenium alloys consist of Pt
0.8Ru
0.2Transmission electron microscope observing shows that nanometer platinum ruthenium alloy particle is the nano particle of hollow, and is evenly distributed in XC-72 nano-sized carbon surface, 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 potassium chloroplatinate and ruthenic chloride, synthetic general platinum-ruthenium alloys/XC-72 nanometer electrical catalyst.The mass fraction of platinum-ruthenium alloys is 9% in the catalyst, platinum-ruthenium alloys consist of Pt
0.8Ru
0.2Transmission electron microscope observing shows Pt in the catalyst
0.8Ru
0.2Nano particle is solid nano particle, and its average grain diameter is 3.8nm.
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.Constant potential polarization is measured the electric current of methyl alcohol electrochemical oxidation on catalyst electrode when 0.04V (with respect to saturated calomel electrode).
The Pt that records in hollow
0.8Ru
0.2The electric current of/XC-72 nanometer electrical catalyst methanol electro-oxidizing is 0.6mA; At general Pt
0.8Ru
0.2The peak current of methanol electro-oxidizing is 0.4mA on the/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:
75 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 50mL sodium borohydride solution, concentration is 0.01mol/L, and reaction is 50 minutes under logical nitrogen protection; Drip 10 milliliters the chloroplatinic acid and the mixed solution of ruthenic chloride then in the synthetic solvent, the concentration of chloroplatinic acid is 0.01mol/L in the mixed solution, the concentration 0.01mol/L of ruthenic chloride, magnetic agitation reaction 60 minutes; Add 70 milligrams of XC-72 nano-sized carbon at last again, continue to lead to nitrogen and stir after 2 hours the mixture in the flask is fully washed with deionized water after filtering,, obtain the platinum ruthenium/XC-72 eelctro-catalyst of hollow 90 ℃ of oven dry.The mass fraction of platinum-ruthenium alloys is 30% in the catalyst, platinum-ruthenium alloys consist of Pt
0.5Ru
0.5Transmission electron microscope observing shows Pt
0.5Ru
0.5Alloy nano particle is the nano particle of hollow, and is evenly distributed on the XC-72 nano-sized carbon carrier, and its average diameter is about 26nm, about the thickness 3.8nm of shell.
As a comparison, directly with the method for sodium borohydride as reducing agent reduction chloroplatinic acid and ruthenic chloride, synthetic general platinum-ruthenium alloys/XC-72 nanometer electrical catalyst.The mass fraction of platinum-ruthenium alloys is 30% in the catalyst, platinum-ruthenium alloys consist of Pt
0.5Ru
0.5Transmission electron microscope observing shows Pt
0.5Ru
0.5Alloy nano particle is solid nano particle, and average grain diameter is 4.1nm.
Carry out the electrocatalysis characteristic test relatively by the method for embodiment 1.
The Pt that records under the same conditions in hollow
0.5Ru
0.5The electric current of methanol electro-oxidizing is 1.2mA on the/XC-72 eelctro-catalyst; At general Pt
0.5Ru
0.5The peak current of methanol electro-oxidizing is 0.8mA on the/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:
90 milliliters of 0.005mol/L cobalt sulfate solutions join in 250 milliliters the three-neck flask, add natrium citricum then, and natrium citricum concentration in synthetic solvent is 0.005mol/L.Constantly stir with magnetic stirring apparatus, and feed nitrogen in synthetic solvent, after 15 minutes, dropwise add the 25mL sodium borohydride solution, concentration is 0.02mol/L, and reaction is 40 minutes under logical nitrogen protection; Drip the mixed solution of 20 milliliters of chloroplatinic acids and ruthenic chloride then in synthetic solvent, the concentration of chloroplatinic acid is 0.005mol/L in the mixed solution, and the concentration of ruthenic chloride is 0.005mol/L, magnetic agitation reaction 45 minutes; Add 70 milligrams of CNTs at last 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, obtains the platinum ruthenium/CNTs eelctro-catalyst of hollow.The mass fraction of platinum-ruthenium alloys is 30% in the catalyst, platinum-ruthenium alloys consist of Pt
0.5Ru
0.5Transmission electron microscope observing shows Pt
0.5Ru
0.5Alloy nano particle is the nano particle of hollow, and is evenly distributed on the CNT, and its average diameter is about 24nm, about the thickness 3.7nm of shell.
As a comparison, directly with the method for sodium borohydride as reducing agent reduction chloroplatinic acid and ruthenic chloride, synthetic general platinum-ruthenium alloys CNTs nanometer electrical catalyst.The mass fraction of platinum-ruthenium alloys is 30% in the catalyst, platinum-ruthenium alloys consist of Pt
0.5Ru
0.5Transmission electron microscope observing shows that nanometer platinum ruthenium alloy particle is solid nano particle in the catalyst, and average grain diameter is 4.3nm.
Carry out the electrocatalysis characteristic test relatively by the method for embodiment 1.
The Pt that records in hollow
0.5Ru
0.5The electric current of methanol electro-oxidizing is 1.3mA on the/CNTs eelctro-catalyst; At general Pt
0.5Ru
0.5The peak current of methanol electro-oxidizing is 0.8mA on the/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 0.005mol/L cobalt chloride solutions join in 250 milliliters the three-neck flask, add polyvinylpyrrolidone then, and polyvinylpyrrolidone concentration in synthetic solvent is 0.005mol/L.Constantly stir with magnetic stirring apparatus, and feed nitrogen in synthetic solvent, after 15 minutes, dropwise add the 12ml sodium borohydride solution, concentration is 0.05mol/L, keeps feeding nitrogen in the course of reaction.Behind the question response 50 minutes, drip 25 milliliters the chloroplatinic acid and the mixed solution of ruthenic chloride again in synthetic solvent, the concentration of chloroplatinic acid is 0.002mol/L in the mixed solution, and the concentration of ruthenic chloride is 0.008mol/L, magnetic agitation reaction 40 minutes.Add 110 milligrams of XC-72 nano-sized carbon at last again, the logical nitrogen of continuation also stirs after 2 hours the mixture in the flask is fully washed with deionized water through filtering the back, 90 ℃ of oven dry, obtains the platinum-ruthenium alloys/XC-72 eelctro-catalyst of hollow.The mass fraction of platinum-ruthenium alloys is 21% in the catalyst, platinum-ruthenium alloys consist of Pt
0.2Ru
0.8Transmission electron microscope observing shows Pt
0.2Ru
0.8Alloy nano particle is the nano particle of hollow, and is evenly distributed on the CNT, and its average diameter is about 27nm, about the thickness 3.9nm of shell.
As a comparison, directly with the method for sodium borohydride as reducing agent reduction chloroplatinic acid and ruthenic chloride, synthetic general platinum-ruthenium alloys/XC-72 nanometer electrical catalyst.The mass fraction of platinum-ruthenium alloys is 21% in the catalyst, platinum-ruthenium alloys consist of Pt
0.2Ru
0.8Transmission electron microscope observing shows Pt
0.2Ru
0.8Nano particle is not the nano particle of hollow, and its average grain diameter is 4.4nm.
Carry out the electrocatalysis characteristic test relatively by the method for embodiment 1.Record at hollow Pt
0.2Ru
0.8The electric current of methanol electro-oxidizing is 0.5mA on the/XC-72 eelctro-catalyst; At general Pt
0.2Ru
0.8The peak current of methanol electro-oxidizing is 0.3mA on the/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 (4)
1. supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst, the nanometer platinum ruthenium alloy particle that it is characterized in that loading on XC-72 nano-sized carbon or carbon nano tube surface is a hollow structure, the atomic ratio that platinum-ruthenium alloys is formed is expressed as Pt
xRu
y, X=0.2～0.8 wherein, Y=0.8～0.2, X+Y=1, the mass fraction of nanometer platinum ruthenium alloy particle is 9%～30% in the catalyst, all the other are XC-72 nano-sized carbon or CNT.
2. the preparation method of supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst 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, add an amount of natrium citricum or polyvinylpyrrolidone as stabilizing agent, making natrium citricum or the polyvinylpyrrolidone concentration 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, and then dropwise add the mixed solution of platinum salt and ruthenium salt, continued stirring reaction 30～60 minutes, the concentration of platinum salt is 0.002～0.05mol/L in the mixed solution, the concentration of ruthenium salt is 0.0005～0.05mol/L, and the ratio of platinum salt and ruthenium salt amount sum and cobalt salt amount is 1: 2～1: 3;
3) add XC-72 nano-sized carbon or carbon nanotube carrier at last and stirred 1～2 hour, after filtration, washing, oven dry, obtain at supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst.
3. the preparation method of the eelctro-catalyst at supported on carbon surface hollow nanometer platinum ruthenium alloy particle according to claim 2 is characterized in that said platinum salt is chloroplatinic acid or potassium chloroplatinate, and ruthenium salt is ruthenic chloride.
4. the preparation method of the eelctro-catalyst at supported on carbon surface hollow nanometer platinum ruthenium alloy particle according to claim 2 is characterized in that said cobalt salt is: cobalt chloride or cobaltous sulfate.
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| CN103579639B (en) * | 2012-07-25 | 2016-06-29 | 中国科学院大连化学物理研究所 | A kind of cathode catalyst for fuel cell and preparation method |
| CN103861582B (en) * | 2012-12-11 | 2016-06-01 | 浙江海洋学院 | The preparation method of a kind of high crystal indices platinum nano catalyst |
| CN109701550A (en) * | 2018-11-27 | 2019-05-03 | 浙江工业大学 | A kind of mesoporous platinum ruthenium film oxygen reduction electro-catalyst of nickel foam self-supporting and preparation method thereof |
| CN111082074A (en) * | 2019-11-28 | 2020-04-28 | 安徽元琛环保科技股份有限公司 | Porous platinum fuel cell catalyst and preparation method thereof |
| CN112206805B (en) * | 2020-10-14 | 2023-05-19 | 扬州大学 | Hollow iron-nickel nitride catalyst, preparation method and full-water electrolysis application thereof |
| CN115415539B (en) * | 2022-08-11 | 2024-06-25 | 华测检测认证集团股份有限公司 | Preparation and application methods of hollow ruthenium copper alloy nano-particles |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318873A (en) * | 2001-05-25 | 2001-10-24 | 中国科学院长春应用化学研究所 | Preparation of nanometer electrical catalyst for protein exchange film fuel cell |
| CN1418725A (en) * | 2002-12-12 | 2003-05-21 | 北方交通大学 | Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube |
| CN1424150A (en) * | 2002-12-27 | 2003-06-18 | 浙江大学 | Method for coating Pt-Ru alloy particles on surface of carbon nano tube |
| JP2003181288A (en) * | 2001-12-13 | 2003-07-02 | Toyota Motor Corp | Method of producing noble metal catalyst |
| WO2005121022A1 (en) * | 2004-06-11 | 2005-12-22 | Tokyo University Of Agriculture And Technology, National University Corporation | Nanocarbon composite structure having ruthenium oxide trapped therein |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318873A (en) * | 2001-05-25 | 2001-10-24 | 中国科学院长春应用化学研究所 | Preparation of nanometer electrical catalyst for protein exchange film fuel cell |
| JP2003181288A (en) * | 2001-12-13 | 2003-07-02 | Toyota Motor Corp | Method of producing noble metal catalyst |
| CN1418725A (en) * | 2002-12-12 | 2003-05-21 | 北方交通大学 | Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube |
| CN1424150A (en) * | 2002-12-27 | 2003-06-18 | 浙江大学 | Method for coating Pt-Ru alloy particles on surface of carbon nano tube |
| WO2005121022A1 (en) * | 2004-06-11 | 2005-12-22 | Tokyo University Of Agriculture And Technology, National University Corporation | Nanocarbon composite structure having ruthenium oxide trapped therein |
Non-Patent Citations (3)
| Title |
|---|
| Preparation and characterization of Pt/C and PtRu/Celectrocatalysts for direct ethanol fuel cells. Zhaolin Liu a,Xing Yi Ling,Xiaodi Sua,et al.Journal of Power Sources,Vol.149 . 2005 * |
| 微波合成PrRu/CNTs催化剂及其电催化性能 韩小斐，陈卫祥，赵杰等.浙江大学学报（工学版），第39卷第12期 2005 * |
| 碳载体的O3处理对直接甲醇燃料电池Pt-Ru/C催化剂性能的影响 王振波，尹鸽平，史鹏飞.化学学报，第63卷第19期 2005 * |
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