CN1827211A - 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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Abstract
The invention discloses a carbon surface carrier hollow platinum ruthenium alloy nanometer particle electric catalyst. Wherein, the platinum ruthenium nanometer particle is in hollow structure; the atom rate of alloy is PtxRuy, while X=0.2-0.8, Y=0.8-0.2 and X+Y=1; the quantity percentage of platinum ruthenium alloy nanometer particle in the catalyst is 9-30%, and the other is carbon. The preparing steps comprises: (1) solving the cobalt salt in the deionized water, adding stabilizer, and feeding nitrogen gas to remove the oxygen in the solution; (2) under the protection of nitrogen gas, adding sodium borohydride solution to deoxidize the cobalt ion into metallic nanometer particle and adding the solution of platinum salt and ruthenium salt to react; (3) adding carbon carrier to be mixed for 1-2 hours, to be filtered, washed and dried to attain the hollow platinum ruthenium/carbon electric catalyst. The inventive catalyst can improve the utilization of platinum and ruthenium, with better electric catalysis property on the electric oxidization of methanol. Therefore, it can be widely used in fuel battery.
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 nanometer platinum ruthenium alloy 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 (6)
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 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.
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, 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 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 described eelctro-catalyst at supported on carbon surface hollow nanometer platinum ruthenium alloy particle according to claim 2, it is characterized in that said platinum salt is: chloroplatinic acid or potassium chloroplatinate, ruthenium salt are 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.
5. 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 carbon carrier is XC-72 nano-sized carbon or CNT.
6. 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 stabilizing agent is natrium citricum or polyvinylpyrrolidone.
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