CN1150998C - Method for coating Pt-Ru alloy particles on surface of carbon nano tube - Google Patents
Method for coating Pt-Ru alloy particles on surface of carbon nano tubeInfo
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- CN1150998C CN1150998C CNB021601925A CN02160192A CN1150998C CN 1150998 C CN1150998 C CN 1150998C CN B021601925 A CNB021601925 A CN B021601925A CN 02160192 A CN02160192 A CN 02160192A CN 1150998 C CN1150998 C CN 1150998C
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- platinum
- carbon nano
- slaine
- ruthenium alloy
- ruthenium
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Abstract
The present invention discloses a method for carrying platinum-ruthenium alloy nano particles on the surfaces of carbon nanotubes. The carbon nanotubes are uniformly dispersed in a polyalcohol solution simultaneously containing two kinds of metal salts of platinum and ruthenium, and then, uniform mixtures of the carbon nanotubes and the metal salts are heated by microwave radiation; each liter of polyalcohol solution of the metal salts contains 0.2 to 8.0g of carbon nanotube, and the concentration of the metal salts in the polyalcohol solution of the metal salts is from 0.0004 to 0.04 mol/l. The carried quantity of the alloy particles on the surfaces of the carbon nanotubes is from 6% to 45%, the atomic composition ratio of alloys is PtxRuy, wherein x is from 0.1 to 1, and y is from 0.1 to 1. The present invention has the advantages that the platinum-ruthenium alloy nano particles carried on the surfaces of the carbon nanotubes have small particle size, the average particle size is from 3 to 3 nm, and the particle size distribution is narrow. The present invention also has the advantages of rapidity, simplicity and high efficiency, and the platinum-ruthenium alloy nano particle materials carried on the carbon nanotubes have extensive application in the fields of electrochemical energy transfer and catalysis.
Description
Technical field
The present invention relates to the preparation of alloy nano particle, relate in particular to a kind of method at carbon nano tube surface load platinum-ruthenium alloy nano particle.
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 fuel cell that DMFC and use contain the hydrogen of micro CO.The nano tubular structure of CNT makes it become a kind of new catalyst carrier, has good catalytic performance in carbon nano tube surface supporting Pt and Ru metallic.By mixed acid carbon nano tube surface is carried out oxidation processes, can improve metal in its surperficial load behavior with nitric acid or sulfuric acid-nitric acid.But general in the past carrying method is an immersion-reduction technique, just at first CNT is immersed in the solution that contains slaine, makes slaine be adsorbed on the surface of CNT, makes its high temperature reduction under reducing atmosphere then.This method is difficult to control load in the size of the metallic particles of carbon nano tube surface and the uniformity of granularity.For example document [1] report adopt immersion-reduction technique in the average grain diameter of the particle of Pd, Pt, Ag and the Au of carbon nano tube surface load respectively 7,8,17,8nm, particle size distribution is at 2 ~ 12nm.And the performance of catalyst is subjected to metal nanoparticle size and inhomogeneity significant impact, and general particle diameter is more little even more, and its catalytic performance is good more.Therefore carbon nano tube surface how load have and littler have practice with the more uniform nano metal particles of size and be worth.
Add hot reflux by the polyhydric alcohol solutions that contains slaine, at high temperature polyalcohol is used at carbon nano tube surface loaded with nano metal particle this polyol process of solution metal ion reduction formation nano particle as reducing agent.Its typical process is to add hot reflux to contain the ethylene glycol solution of slaine and the mixture of CNT, and the reducing agent of ethylene glycol generation at high temperature makes the metal ion reduction and loads on the surface of CNT.But this traditional hot reflux that adds needs 1-3h, also is not easy to control the size of final nano particle.
Document [1] Xue B, Chen P, Hong Q, Lin JY, Tan KL, Growth of Pd, Pt, Ag and Aunanoparticles on carbon nanotubes, JOURNAL OF MATERIALS CHEMISTRY11 (9): 2378-2381 2001.
Summary of the invention
The purpose of this invention is to provide a kind of method at carbon nano tube surface load platinum-ruthenium alloy nano particle.
It is with even carbon nanotube be dispersed in the polyhydric alcohol solutions that contains platinum and two kinds of slaines of ruthenium simultaneously, then with the homogeneous mixture of this CNT of carry out microwave radiation heating and slaine polyhydric alcohol solutions; The polyhydric alcohol solutions of per 1 liter slaine contains 0.2~8.0 gram CNT; The concentration of slaine is 0.0004~0.04 mol in the slaine polyhydric alcohol solutions; The composed atom of alloy is than being Pt
xRu
y, X=0.1~1 wherein, Y=0.1~1; Polyalcohol is 7 glycol.
Advantage of the present invention is that the platinum-ruthenium alloy nano particle diameter in the carbon nano tube surface load is tiny, and average grain diameter is in the 3-4 nanometer, and has narrow grain through Size Distribution.Alloy particle is 6%~45% in the load capacity of carbon nano tube surface.The present invention also has fast, and is simple, the advantage that efficient is high.This carbon nanotube loaded platinum-ruthenium alloy nanometer particle material has utilization widely in electrochemical energy conversion and catalytic field.
The specific embodiment
Wherein a kind of slaine of above-mentioned two kinds of slaines is: chloroplatinic acid, potassium chloroplatinate or platinum acetate; Another slaine is a ruthenic chloride; CNT is multi-walled carbon nano-tubes or SWCN.
Embodiment 1:
The multi-walled carbon nano-tubes of 0.08 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.0001 mole of chloroplatinic acid and 0.0001 mole of ruthenic chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum-ruthenium alloy particle of transmission electron microscope observing carbon nanometer tube area load is at 3.4nm, and grain is through being distributed between 2~4nm.The composition of platinum-ruthenium alloy is: Pt
1.0Ru
1.0Platinum-ruthenium alloy is 26% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum-ruthenium alloy particle of traditional immersion-method of reducing preparation at 6.4nm, grain is through being distributed between the 1-13nm.
Embodiment 2:
The multi-walled carbon nano-tubes of 0.01 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.00001 mole of chloroplatinic acid and 0.00001 mole of ruthenic chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum-ruthenium alloy particle of transmission electron microscope observing carbon nano tube surface load is at 3.1nm, and grain is through being distributed between 2~4nm. and the composition of platinum-ruthenium alloy is: Pt
1.0Ru
1.0Platinum-ruthenium alloy is 22% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum-ruthenium alloy particle of traditional immersion-method of reducing preparation at 6.0nm, grain is through being distributed between 1~10nm.
Embodiment 3:
The multi-walled carbon nano-tubes of 0.4 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.0001 mole of chloroplatinic acid and 0.0001 mole of ruthenic chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum-ruthenium alloy particle of transmission electron microscope observing carbon nano tube surface load is at 3.5nm, and grain is through being distributed between 2~4nm. and the composition of platinum-ruthenium alloy is: Pt
1.0Ru
1.0Platinum-ruthenium alloy is 6.9% in the load capacity of carbon nano tube surface.And with the average grain diameter of the nanometer platinum-ruthenium alloy particle of the carbon nanometer tube load of traditional immersion-method of reducing preparation at 7.4nm, grain is through being distributed between 1~12nm.
Embodiment 4:
The multi-walled carbon nano-tubes of 0.4 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.001 mole of chloroplatinic acid and 0.001 mole of ruthenic chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum-ruthenium alloy particle of transmission electron microscope observing carbon nano tube surface load is at 3.6nm, and grain is through being distributed between 2~5nm. and the composition of platinum-ruthenium alloy is: Pt
1.0Ru
1.0Platinum-ruthenium alloy is 42% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum-ruthenium alloy particle of traditional immersion-method of reducing preparation at 7.4nm, grain is through being distributed between 1~15nm.
Embodiment 5:
The SWCN of 0.08 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.0001 mole of potassium chloroplatinate and 0.00001 mole of ruthenic chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum-ruthenium alloy particle of transmission electron microscope observing carbon nano tube surface load is at 3.3nm, and grain is through being distributed between 2~4nm. and the composition of platinum-ruthenium alloys is: Pt
1.0Ru
1.0Platinum-ruthenium alloy is 20% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum-ruthenium alloy particle of traditional immersion-method of reducing preparation at 5.4nm, grain is through being distributed between 1~11nm.
Embodiment 6:
The SWCN of 0.08 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.00001 molar acetate platinum and 0.0001 mole of ruthenic chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum-ruthenium alloy particle of transmission electron microscope observing carbon nano tube surface load is at 3.3nm, and grain is through being distributed between 2~4nm. and the composition of platinum-ruthenium alloys is: Pt
0.1Ru
1.0Platinum-ruthenium alloy is 13% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum-ruthenium alloy particle of traditional immersion-method of reducing preparation at 5.4nm, grain is through being distributed between 1~11nm.
Claims (3)
1. method at carbon nano tube surface load platinum-ruthenium alloy nano particle, it is characterized in that with even carbon nanotube be dispersed in the polyhydric alcohol solutions that contains platinum and two kinds of slaines of ruthenium simultaneously, then with the homogeneous mixture of this CNT of carry out microwave radiation heating and slaine polyhydric alcohol solutions; The polyhydric alcohol solutions of per 1 liter slaine contains 0.2~8.0 gram CNT; The concentration of slaine is 0.0004~0.04 mol in the slaine polyhydric alcohol solutions; The composed atom of alloy is than being Pt
xRu
y, X=0.1~1 wherein, Y=0.1~1; Polyalcohol is an ethylene glycol.
2. a kind of method at carbon nano tube surface load platinum-ruthenium alloy nano particle according to claim 1 is characterized in that wherein a kind of slaine of said two kinds of slaines is: chloroplatinic acid, potassium chloroplatinate or platinum acetate; Another slaine is a ruthenic chloride.
3. a kind of method at carbon nano tube surface load platinum-ruthenium alloy nano particle according to claim 1 is characterized in that CNT is multi-walled carbon nano-tubes or SWCN.
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JP3624196B1 (en) * | 2004-02-20 | 2005-03-02 | 株式会社フルヤ金属 | Particle dispersion composite and solid electrolyte sensor using the same |
CN100434167C (en) * | 2005-11-17 | 2008-11-19 | 上海交通大学 | Method for preparing carbon nanometer material carried with noble metal(S) |
CN100424061C (en) * | 2006-02-23 | 2008-10-08 | 华南理工大学 | Alcohol liquid phase catalytic oxidation method and catalyst reactivation method |
CN100346876C (en) * | 2006-04-14 | 2007-11-07 | 浙江大学 | Electrocatalyst with hollow nanometer platinum ruthenium alloy particle supported on carbon surface and its preparing method |
CN100464841C (en) * | 2006-12-29 | 2009-03-04 | 华东理工大学 | Noble metal electrocatalyst based on nano carbon fiber and its preparing method |
CN102990080B (en) * | 2012-12-05 | 2014-12-31 | 黑龙江大学 | Method for preparing carbon nanotube-loaded nano-copper-nickel solid solution by utilizing microwave |
CN111939908A (en) * | 2020-07-03 | 2020-11-17 | 南方科技大学 | Molybdenum-ruthenium alloy catalyst and preparation method and application thereof |
CN114049984B (en) * | 2021-12-28 | 2022-03-29 | 西安宏星电子浆料科技股份有限公司 | Low-cost low-resistance chip resistor paste |
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