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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- platinum
- carbon nano
- slaine
- ruthenium alloy
- ruthenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 7
- 239000000956 alloy Substances 0.000 title claims abstract description 7
- 239000002245 particle Substances 0.000 title abstract description 23
- 229910002848 Pt–Ru Inorganic materials 0.000 title 1
- 239000011248 coating agent Substances 0.000 title 1
- 238000000576 coating method Methods 0.000 title 1
- 229910000929 Ru alloy Inorganic materials 0.000 claims abstract description 37
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 claims abstract description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 230000005855 radiation Effects 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Chemical class 0.000 claims abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 2
- 239000008240 homogeneous mixture Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract 5
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052709 silver 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QCSGLAMXZCLSJW-UHFFFAOYSA-L platinum(2+);diacetate Chemical compound [Pt+2].CC([O-])=O.CC([O-])=O QCSGLAMXZCLSJW-UHFFFAOYSA-L 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
Landscapes
- Inert Electrodes (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Catalysts (AREA)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021601925A CN1150998C (en) | 2002-12-27 | 2002-12-27 | Method for coating Pt-Ru alloy particles on surface of carbon nano tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021601925A CN1150998C (en) | 2002-12-27 | 2002-12-27 | Method for coating Pt-Ru alloy particles on surface of carbon nano tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424150A CN1424150A (en) | 2003-06-18 |
| CN1150998C true CN1150998C (en) | 2004-05-26 |
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|---|---|---|---|
| CNB021601925A Expired - Fee Related CN1150998C (en) | 2002-12-27 | 2002-12-27 | Method for coating Pt-Ru alloy particles on surface of carbon nano tube |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2002
- 2002-12-27 CN CNB021601925A patent/CN1150998C/en not_active Expired - Fee Related
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| CN1424150A (en) | 2003-06-18 |
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