CN1150997C - Method for coating mono-metal particles on carbon nano tube surface - Google Patents
Method for coating mono-metal particles on carbon nano tube surfaceInfo
- Publication number
- CN1150997C CN1150997C CNB021601917A CN02160191A CN1150997C CN 1150997 C CN1150997 C CN 1150997C CN B021601917 A CNB021601917 A CN B021601917A CN 02160191 A CN02160191 A CN 02160191A CN 1150997 C CN1150997 C CN 1150997C
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- tubes
- slaine
- tube surface
- nano tube
- 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
Abstract
The present invention discloses a method for carrying nanometer monometallic particles on the surfaces of carbon nano-tubes, and metal is Pt, Pd, Ru, Au and Ag. The carbon nano-tubes are uniformly dispersed in a polyalcohol solution of one kind of metallic salts, and uniform mixtures of the carbon nano-tubes and the polyalcohol solution of the metallic salts are heated by microwave radiation; 1 liter of polyalcohol solution of the metallic salts contains 0.2 to 8g of carbon nano-tube; the concentration of the metallic salts of the polyalcohol solution of the metallic salts is from 0.0002 to 0.03 mol/l; the carried quantity of the metallic particles on the surfaces of the carbon nano-tubes is from 5% to 42%. The present invention has the advantages that the nanometer metallic particles carried on the surfaces of the carbon nano-tubes have small particle size, the average particle size of the nanometer metallic particles is from 3 to 4 nm, and the nanometer metallic particles have narrow particle size distribution. The present invention also has the advantages of rapidity, simplicity and high efficiency, and the materials of the nanometer metallic particles carried on the carbon nano-tubes have extensive application in the fields of electrochemical energy transfer and catalysis.
Description
Technical field
The present invention relates to the preparation of nano metal particles, relate in particular to a kind of method at carbon nano tube surface loaded with nano monometallic particle.
Background technology
CNT has excellent physics and chemical property with its particular structure, has utilization widely.The nano tubular structure of CNT makes it become a kind of new catalyst carrier, for example has good catalytic performance at metallics such as carbon nano tube surface supporting Pt and Ru.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.What but carrying method in the past still adopted is general immersion-reduction technique, just at first the CNT after handling is immersed in the solution that contains slaine, make slaine be adsorbed on the surface (the interior pipe that enters CNT is also arranged) of CNT, make its high temperature reduction under reducing atmosphere then.The method that also can adopt vapour deposition and chemical plating in addition is in carbon nano tube surface burden metal nanoparticle or nanometer film.But these methods are difficult to the size of control load at the metallic particles of carbon nano tube surface, and it distributes also than broad.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 precious metal salt 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 loaded with nano monometallic particle.
It is that even carbon nanotube is dispersed in a kind of polyhydric alcohol solutions of slaine, adopts the homogeneous mixture of this CNT of carry out microwave radiation heating and slaine polyhydric alcohol solutions then.The polyhydric alcohol solutions of per 1 liter slaine contains 0.2～8 gram CNT; The concentration of slaine is 0.0002～0.03 mol in the slaine polyhydric alcohol solutions; Slaine is: chloroplatinic acid, potassium chloroplatinate, platinum acetate, ruthenic chloride, gold chloride, silver nitrate, palladium bichloride=or palladium; The metal of institute's load is on CNT accordingly: Pt, Pd, Ru, Au=or Ag; Polyalcohol is an ethylene glycol.
Advantage of the present invention is tiny at the Pt of carbon nano tube surface load, Pd, Ru, Au or Ag metal nanoparticle particle diameter, and average grain diameter is in 3～4 nanometers, and has narrow grain through Size Distribution.Metallic is 5%～42% in the load capacity of carbon nano tube surface.The present invention also has fast, and is simple, the advantage that efficient is high.The material of this carbon nanotube loaded metal nanoparticle has utilization widely in electrochemical energy conversion and catalytic field.
The specific embodiment
Above-mentioned slaine is: chloroplatinic acid, potassium chloroplatinate, platinum acetate, ruthenic chloride, gold chloride, silver nitrate, palladium bichloride or palladium; Polyalcohol is an ethylene glycol; 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 uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum particles of transmission electron microscope observing carbon nano tube surface load is at 3.5nm, and grain is through being distributed between the 2-4nm. and platinum nanoparticles is 19% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum particles of traditional immersion-method of reducing preparation at 7.6nm, grain is through being distributed between the 2-11nm.
Embodiment 2:
The SWCN of 0.01 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.00001 molar acetate platinum uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum particles of transmission electron microscope observing carbon nano tube surface load is at 3.3nm, grain is through being distributed between the 2-4nm, and platinum nanoparticles is 16% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum particles of traditional immersion-method of reducing preparation at 6.6nm, grain is through being distributed between the 1-9nm.
Embodiment 3:
The multi-walled carbon nano-tubes of 0.4 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.0015 mole of potassium chloroplatinate uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer platinum particles of transmission electron microscope observing carbon nano tube surface load is at 3.6nm, grain is through being distributed between the 2-4nm, and platinum nanoparticles is 42% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer platinum particles of traditional immersion-method of reducing preparation at 7.8nm, grain is through being distributed between the 1-13nm.
Embodiment 4:
The multi-walled carbon nano-tubes of 0.02 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.00005 mole of ruthenic chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer ruthenium particle of transmission electron microscope observing carbon nano tube surface load is at 3.2nm, grain is through being distributed between the 2-4nm, and the ruthenium metal nanoparticle is 20% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer ruthenium particle of traditional immersion-method of reducing preparation at 6.1nm, grain is through being distributed between the 1-9nm.
Embodiment 5:
The multi-walled carbon nano-tubes of 0.09 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.00005 molar acetate palladium uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nanometer palladium particle of transmission electron microscope observing carbon nano tube surface load is at 3.8nm, grain is through being distributed between the 2-4.2nm, and the palladium metal nano particle is 5.5% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nanometer palladium particle of traditional immersion-method of reducing preparation at 6.8nm, grain is through being distributed between the 1-12.3nm.
Embodiment 6:
The multi-walled carbon nano-tubes of 0.09 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.00005 mole of gold chloride uniformly, heating is 1 minute under 700 watts microwave radiation. and the average grain diameter of the nano Au particle of transmission electron microscope observing carbon nano tube surface load is at 3.5nm, grain is through being distributed between the 2-4nm, and metal nanoparticle is 10% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nano Au particle of traditional immersion-method of reducing preparation at 7.6nm, grain is through being distributed between the 2-11nm.
Embodiment 7:
The multi-walled carbon nano-tubes of 0.04 gram is dispersed in 50 milliliters the ethylene glycol solution that contains 0.00005 equimolar silver nitrate uniformly, and heating is 1 minute under 700 watts microwave radiation.The average grain diameter of the nano silver particles of transmission electron microscope observing carbon nano tube surface load is at 3.4nm, and grain is through being distributed between the 2-4nm, and the silver metal nano particle is 11% in the load capacity of carbon nano tube surface.And with the average grain diameter of the carbon nanotube loaded nano silver particles of traditional immersion-method of reducing preparation at 6.0nm, grain is through being distributed between the 1-9nm.
Claims (2)
1. the method at carbon nano tube surface loaded with nano monometallic particle is characterized in that even carbon nanotube is dispersed in the slaine polyhydric alcohol solutions, adopts the homogeneous mixture of this CNT of carry out microwave radiation heating and slaine polyhydric alcohol solutions then; The polyhydric alcohol solutions of per 1 liter slaine contains 0.2～8 gram CNT; The concentration of slaine is 0.0002～0.03 mol in the slaine polyhydric alcohol solutions, and slaine is: chloroplatinic acid, potassium chloroplatinate, platinum acetate, ruthenic chloride, gold chloride, silver nitrate, palladium bichloride or palladium; The metal of institute's load is on CNT accordingly: Pt, Pd, Ru, Au or Ag, polyalcohol are ethylene glycol.
2, according to the described a kind of method of claim 1, it is characterized in that said CNT is: multi-walled carbon nano-tubes or SWCN at carbon nano tube surface loaded with nano monometallic particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021601917A CN1150997C (en) | 2002-12-27 | 2002-12-27 | Method for coating mono-metal particles on carbon nano tube surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021601917A CN1150997C (en) | 2002-12-27 | 2002-12-27 | Method for coating mono-metal particles on carbon nano tube surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424149A CN1424149A (en) | 2003-06-18 |
| CN1150997C true CN1150997C (en) | 2004-05-26 |
Family
ID=4753413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021601917A Expired - Fee Related CN1150997C (en) | 2002-12-27 | 2002-12-27 | Method for coating mono-metal particles on carbon nano tube surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1150997C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109395719A (en) * | 2018-11-05 | 2019-03-01 | 江苏大学 | A method of in multi-wall carbon nano-tube pipe surface controllable load noble metal nanometer material |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005005687A1 (en) * | 2003-07-02 | 2005-01-20 | Seldon Technologies, Llc | Method of coating nanosturctures with metal using metal salts |
| CN100336596C (en) * | 2005-04-08 | 2007-09-12 | 浙江大学 | Preparation method for loading platinum nanoparticles on carbon carrier |
| CN100432015C (en) * | 2005-05-27 | 2008-11-12 | 上海大学 | Preparation method of multi-wall nanometer carbon tube conductive material for switch contact device |
| CN100371079C (en) * | 2005-12-05 | 2008-02-27 | 浙江大学 | Method for preparing platinum/carbon nano electro catalyst by microwave synthesis |
| CN100443167C (en) * | 2006-11-02 | 2008-12-17 | 上海交通大学 | Method for reduce deposition of high dispersible Pt catalyst granule in batches |
| CN101290310B (en) * | 2007-04-20 | 2012-01-11 | 中国科学院大连化学物理研究所 | Piezoelectric type hydrogen sensor and its preparation and uses |
| CN100464845C (en) * | 2007-07-17 | 2009-03-04 | 浙江大学 | Method of synthesizing Pt-CeO*/C electro-catalyst with one-step method microwave |
| CN101433840B (en) * | 2007-11-12 | 2011-02-16 | 中国科学院理化技术研究所 | Carbon nano-tube microparticle supported palladium nano particle as well as preparation method and application thereof |
| CN101444730B (en) * | 2007-11-27 | 2011-07-27 | 北京化工大学 | Method for preparing carbon nano-fiber/silver nano-particle composite catalyst |
| CN101249435B (en) * | 2008-03-25 | 2010-06-02 | 中山大学 | Surface treating method of carbon nano-tube and loading type catalyst of carbon nano-tube |
| CN101683978B (en) * | 2008-06-09 | 2012-05-30 | 香港科技大学 | Method for preparing carbon nano tube modified by silver nano particles |
| CN108452790B (en) | 2011-07-26 | 2022-05-03 | 1D材料公司 | Nanostructured battery active materials and methods of making the same |
| 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 |
| CN104056622B (en) * | 2013-03-20 | 2017-02-08 | 中国科学院大连化学物理研究所 | Rhodium/carbon nanotube catalyst and preparation method and application |
| CN103223339A (en) * | 2013-04-09 | 2013-07-31 | 中国科学院福建物质结构研究所 | Method for preparing supported Pd-based catalysts |
| CN104248950A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院大连化学物理研究所 | Palladium/carbon nanotube catalyst and preparation and application thereof |
| CN104300112B (en) * | 2013-07-18 | 2016-12-28 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell positive pole |
| CN104588644B (en) * | 2015-01-20 | 2016-03-16 | 宁波卡尔新材料科技有限公司 | The method of the nano carbon particle of microwave irradiation synthesis load Au |
| CN105214653B (en) * | 2015-08-28 | 2018-09-21 | 北京化工大学 | A kind of preparation method of carbon nanotube loaded nanoparticle catalyst |
| KR20180122319A (en) * | 2016-01-15 | 2018-11-12 | 니폰 제온 가부시키가이샤 | A composition for a thermoelectric conversion element, a method for producing a carbon nanotube on which metal nanoparticles are supported, a molded article for a thermoelectric conversion element, a method for producing the same, |
| EP4292702A3 (en) | 2016-07-15 | 2024-04-17 | OneD Material, Inc. | Manufacturing apparatus and method for making silicon nanowires on carbon based powders for use in batteries |
| KR101971260B1 (en) * | 2016-09-26 | 2019-04-22 | 충남대학교산학협력단 | Preparation Method for Cdot-Pt-Pd Composite, Cdot-Pt-Pd Catalyst thereby and Fuel Cell using the Catalyst |
| CN107658475A (en) * | 2017-09-25 | 2018-02-02 | 青岛大学 | A kind of platinum/black phosphorus@carbon ball methanol fuel cell anode catalyzers and preparation method thereof |
| CN107986382A (en) * | 2017-12-07 | 2018-05-04 | 北京科瑞博远科技有限公司 | A kind of method of microwave irradiation high concentrated organic wastewater |
| CN109911884A (en) * | 2019-05-05 | 2019-06-21 | 国网重庆市电力公司电力科学研究院 | A method of preparing platinum dopant carbon nanotube |
| CN112034015A (en) * | 2020-09-04 | 2020-12-04 | 西南大学 | Platinum-palladium doped CNT (carbon nanotube), and preparation method and application of doped CNT sensor |
| CN112014440B (en) * | 2020-09-04 | 2022-02-01 | 西南大学 | Preparation method and application of platinum nitrogen doped CNT (carbon nanotube) and doped CNT sensor |
| CN114522242B (en) * | 2022-02-28 | 2023-02-03 | 深圳大学 | Magnetic drive spiral micro-nano motor and preparation method and application thereof |
-
2002
- 2002-12-27 CN CNB021601917A patent/CN1150997C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109395719A (en) * | 2018-11-05 | 2019-03-01 | 江苏大学 | A method of in multi-wall carbon nano-tube pipe surface controllable load noble metal nanometer material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1424149A (en) | 2003-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1150997C (en) | Method for coating mono-metal particles on carbon nano tube surface | |
| Cornelio et al. | Palladium nanoparticles on carbon nanotubes as catalysts of cross-coupling reactions | |
| Saha et al. | Functionalizing carbon nanotubes for proton exchange membrane fuel cells electrode | |
| WO2021017966A1 (en) | Supported ultrafine alloy nanoparticle and preparation method therefor and application thereof | |
| Pan et al. | Reactions over catalysts confined in carbon nanotubes | |
| Bai et al. | Graphene–inorganic nanocomposites | |
| Zhang et al. | Porous dendritic platinum nanotubes with extremely high activity and stability for oxygen reduction reaction | |
| Esmaeilifar et al. | Synthesis methods of low-Pt-loading electrocatalysts for proton exchange membrane fuel cell systems | |
| Ang et al. | Electroless plating of metals onto carbon nanotubes activated by a single-step activation method | |
| CN1918067B (en) | A method for the preparation of y-branched carbon nanotubes | |
| Shi et al. | Easy decoration of carbon nanotubes with well dispersed gold nanoparticles and the use of the material as an electrocatalyst | |
| CN101837287B (en) | Preparation of carbon nano-tube nano-particle composite material | |
| Yu et al. | Coating MWNTs with Cu2O of different morphology by a polyol process | |
| Gao et al. | Facile and large-scale synthesis and characterization of carbon nanotube/silver nanocrystal nanohybrids | |
| Tsai et al. | Enhancing hydrogen storage on carbon nanotubes via hybrid chemical etching and Pt decoration employing supercritical carbon dioxide fluid | |
| CN112553646A (en) | MXene loaded nano alloy catalyst, preparation method and application thereof | |
| Wen et al. | Monodispersed gold nanoparticles supported on γ-Al2O3 for enhancement of low-temperature catalytic oxidation of CO | |
| WO2010005548A2 (en) | Functionalization of carbon nanotubes with metallic moieties | |
| JP4861849B2 (en) | Method for producing platinum catalyst supported on carbon nanotubes by chemical vapor deposition | |
| CN101716507A (en) | Preparation method of platiniridium/carbon-electro catalyst by using microwave synthesis | |
| CN1150998C (en) | Method for coating Pt-Ru alloy particles on surface of carbon nano tube | |
| Hossain | Bimetallic Pd–Fe supported on nitrogen-doped reduced graphene oxide as electrocatalyst for formic acid oxidation | |
| CN100336596C (en) | Preparation method for loading platinum nanoparticles on carbon carrier | |
| CN112588287A (en) | Method for synthesizing carbon material loaded Pt nano-particle material by ultraviolet illumination | |
| CN111417596B (en) | Fibrous carbon nanostructure, method for evaluating the same, and method for producing surface-modified product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |