CN102614891A - Preparation method of precious metal modified binary alloys catalyst - Google Patents
Preparation method of precious metal modified binary alloys catalyst Download PDFInfo
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- CN102614891A CN102614891A CN2011100352420A CN201110035242A CN102614891A CN 102614891 A CN102614891 A CN 102614891A CN 2011100352420 A CN2011100352420 A CN 2011100352420A CN 201110035242 A CN201110035242 A CN 201110035242A CN 102614891 A CN102614891 A CN 102614891A
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Abstract
The invention relates to a preparation method that precious metal is subjected to surface modification on the binary alloys (one is non-precious metal) nano particles to obtain a novel catalysis material, which belongs to the catalyst preparation technical field. The invention is characterized in that the material takes chloroplatinic acid, palladium chloride, cupric chloride, cobaltous chloride, iron chloride, potassium permanganate, monosodium glutamate, glycol and potassium borohydride as raw materials. A metal alloy catalyst is loaded on the surface of a carbon carrier, then the precious metal nano particles modify the binary alloys nano particles surface to obtain the novel catalysis material. According to the invention, the prepared novel catalysis material of the binary alloys nano particles possesses uniform particle size, is uniformly loaded on the carbon carrier surface, possesses good electrocatalytic activity, and has wide application prospect in the proton exchange membrane fuel cell catalyst field. The whole preparation process has the advantages of good environment, simple equipment and easy realization, thereby the method of the invention is an ideal method for preparing the high efficient and cheap catalysis material.
Description
Technical field
The present invention relates to fuel-cell catalyst and preparing technical field thereof, the alloy nanoparticle of promptly with a kind of noble metal other two kinds of metals being formed carries out finishing and the new catalytic material that obtains.
Background technology
Fuel cell becomes the ideal source that adapts to future source of energy and environmental requirement, at present in industry example use such as the vehicles, cellular phone power supplies owing to have advantages such as energy conversion efficiency height, environmental pollution are little.Yet the expensive price of new fuel cell catalyst platinum is one of major obstacle of its industrialization of restriction, and therefore, inquiring into the cost, the raising activity of such catalysts that how to reduce catalyst is the current research focus in this field.We consider from following two aspects to this problem: at first, reduce the consumption of metal platinum, to reduce the catalyst cost; Secondly, further improve activity of such catalysts and utilization rate.It is the effective way that reduces cost, improves catalytic activity that other noble metal and base metal and platinum are processed alloy catalyst.EP450849 discloses binary and ternary platinum alloy catalysts and the purposes in fuel cell thereof.CN101014410A discloses the ternary platinum alloy catalysts that can be used as fuel-cell catalyst.But the noble metal platinum in these catalyst is not all on the surface, because catalytic action occurs in the microstructure surface of reactive metal, so its utilization rate still awaits further raising.Electrochimica Acta2010; 55; Introduce the synthetic platinum modification of solvent-thermal method palladium-nickel alloy nucleocapsid structure in 1519 and made oxygen reduction catalyst; This method makes that the utilization rate of noble metal is further enhanced in the catalyst, and still, nucleocapsid structure can not be brought the advantage of nuclear metal into play well.The present invention is intended to use a kind of noble metal nano particles; (as: platinum); Bianry alloy (wherein a kind of the is base metal) nano particle that other two kinds of metals are formed carries out finishing; Can more noble metal be exposed to the microstructure surface of nano material, and the advantages such as high catalytic activity of alloy catalyst are able to simultaneously embody.This new catalytic material improves catalyst activity and utilization rate on the basis of the consumption that reduces metal platinum, effectively reduce the fuel-cell catalyst cost.
Summary of the invention
Main contents of the present invention have been to provide a kind of and have carried out the synthetic method that finishing obtains catalyst through the synthetic alloy nano catalyst granules that a kind of noble metal is formed other two kinds of metals of two steps; This method reaction condition environmental friendliness, instrument and equipment are simple; And synthetic catalyst is on the basis of the consumption that reduces metal platinum, and catalytic activity and utilization rate will effectively improve.This experiment was divided into for two steps: at first be in carbon carrier area load metal alloy catalyst, with a kind of noble metal alloy nanoparticle carried out finishing then and the new catalytic material that obtains.
Its key step is following:
1. will contain noble metal and non-noble metal two kinds of metal salt solutions and amino acid and in week reduction solution, mix, make mixed solution;
2. to the mixed solution and dripping dilute alkaline soln, the adjustment system pH makes metal ion and the abundant chelating of amino acid radical ion to alkalescence (8-14);
3. in above-mentioned system, add an amount of carbon carrier, fully stir, again mixture is changed in the autoclave, with the autoclave sealing, reaction 1-70h under 110-300 ℃;
4. naturally cool to room temperature then, with the black precipitate that obtains fully wash, drying, can obtain metal alloy nanoparticle;
5. above-mentioned alloy nanoparticle is scattered in the water alcohol mixed liquor, stirs, add an amount of metal platinum saline solution, slowly drip strong reducing property solution under the stirring condition again to system;
6. after above-mentioned system was fully reacted, washing, drying obtained target product.
The useful effect that the present invention has is:
1. be reflected in the aqueous solution and the alcoholic solution and carry out, mild condition, environmental friendliness;
2. reaction unit and technological operating procedure are simple;
3. the synthetic catalyst of this invention has reduced the consumption of metal platinum, effectively reduces the fuel-cell catalyst cost, and catalytic activity and utilization rate are improved, for the preparation of the fuel-cell catalyst of efficient and cheap provides experimental program and foundation;
4. can change metal alloy according to actual needs;
5. this catalyst is significantly improved to the methanol oxidation electro catalytic activity, has broad application prospects in the DMFC catalyst field.
In a word, the present invention has advantages such as the fuel-cell catalyst of reduction cost, through changing reaction condition, can regulate the particle diameter and the dispersiveness of metal alloy nanoparticle, further improves the utilization rate of catalyst.
The practical implementation example
Examples of implementation 1:
(1) gets PdCl
2(0.2M, 3.8mL), 19mg CoCl
2Join in the 40mL ethylene glycol with 50mg glutamic acid and to mix, make mixed solution;
(2) to mixed solution and dripping 0.5M NaOH solution, adjustment system pH to 9 makes metal ion and the abundant chelating of glutamate ion;
(3) in above-mentioned system, add 30mg multi-walled carbon nano-tubes (MWCNTs) carrier, fully stir, mixture being changed over to the polytetrafluoroethylene (PTFE) is in the 50mL autoclave of liner again, with the autoclave sealing, keeps 68h down at 120 ℃;
(4) naturally cool to room temperature then, with the black precipitate that obtains fully wash, drying, can obtain the PdCo/MWCNTs alloy catalyst; Sample is through technical Analysis such as XRD, transmission electron microscope, cyclic voltammetrics.The result shows that average grain diameter is that PdCo alloy nanoparticle about 7.2nm is dispersed in MWCNTs surface (Fig. 1).
(5) PdCo/MWCNTs powder art is scattered among the mixed liquor 100mL of ethylene glycol and water (1: 1), stirs, add an amount of H to system
2PtCl
6The aqueous solution slowly drips 0.1mol/L 50mL reducing agent KBH again under the stirring condition
4The aqueous solution;
(6) after above-mentioned system was fully reacted, washing, drying obtained target product.Product is through technical Analysis such as XRD, transmission electron microscope, EDS, cyclic voltammetrics.The result has been illustrated on the PdCo alloy nano granule surface deposition Pt nano particle (Fig. 1), and its electrocatalysis characteristic is significantly improved.
Examples of implementation 2:
(1) gets PdCl
2(0.2M, 4.5mL), 30mg CuCl
22H
2Mix in O and the 100mg histidine adding 40mL butanediol, make mixed solution;
(2) to mixed solution and dripping 0.5M KOH solution, adjustment system pH to 10 makes metal ion and the abundant chelating of histidine radical ion;
(3) in above-mentioned system, add 30mg carrier MWCNTs, fully stir, mixture being changed over to the polytetrafluoroethylene (PTFE) is in the 50mL autoclave of liner again, with the autoclave sealing, keeps 30h down at 200 ℃;
(4) naturally cool to room temperature then, with the black precipitate that obtains fully wash, drying, can obtain the PdCu/MWCNTs alloy catalyst;
(5) the PdCu/MWCNTs powder is scattered among the mixed liquor 100mL of ethylene glycol and water, stirs, add an amount of H to system
2PtCl
6The aqueous solution slowly drips 0.1mol/L 50mL reducing agent KBH again under the stirring condition
4The aqueous solution;
(6) after above-mentioned system was fully reacted, washing, drying obtained target product.
Examples of implementation 3:
(1) gets PdCl
2(0.2M, 6mL), 60mg KMnO
4Add in the 40mL ethylene glycol with 80mg glutamic acid and to mix, make mixed solution;
(2) to mixed solution and dripping 0.5M NaOH solution, adjustment system pH to 12 makes metal ion and the abundant chelating of glutamate ion;
(3) in above-mentioned system, add 30mg carrier MWCNTs, fully stir, mixture being changed over to the polytetrafluoroethylene (PTFE) is in the 50mL autoclave of liner again, with the autoclave sealing, keeps 60h down at 160 ℃;
(4) naturally cool to room temperature then, with the black precipitate that obtains fully wash, drying, can obtain the PdMn/MWCNTs alloy catalyst; Sample is through technical Analysis such as XRD, transmission electron microscope, cyclic voltammetrics.
(5) the PdMn/MWCNTs powder is scattered among the mixed liquor 100mL of ethylene glycol and water (1: 1), stirs, add an amount of H to system
2PtCl
6The aqueous solution slowly drips 0.05mol/L 80mL reducing agent ammonia spirit again under the stirring condition;
(6) after above-mentioned system was fully reacted, washing, drying obtained target product.
Description of drawings
Fig. 1. transmission electron microscope (TEM) photo and corresponding its granularmetric analysis of catalysis material in the embodiment of the invention son 1: (a, c) Pd/MWCNTs catalyst, (b, d) Pt-PdCo/MWCNTs catalyst
Fig. 2. be the EDS ability spectrogram of catalysis material material Pt-PdCo/MWCNTs in the embodiment of the invention son 1;
Fig. 3. be the XRD figure of catalysis material in the embodiment of the invention son 1: (a) Pt-PdCo/MWCNTs, (b) PdCo/MWCNTs, (c) Pd/MWCNTs and (d) Pt/MWCNTs;
Fig. 4. catalysis material (a) Pt-PdCo/MWCNTs in the embodiment of the invention son 1, (b) JM 20%commercial Pt/C and (c) Pt/MWCNTs are at 0.5M H
2SO
4With 0.5M CH
3Cyclic voltammetry curve in the mixed solution of OH, sweep speed 50mV/s, 25 ℃.
Claims (10)
1. a binary alloy nano particle of other two kinds of metals being formed with noble metal carries out the preparation method that finishing obtains ternary metallic catalyst; It is characterized in that: at first a certain amount of two metal ion species solution and amino acid carry out chelating in week reduction solution; Use dilute alkaline soln to regulate pH value then and be 8-14, add an amount of carbon carrier, in the autoclave that stirs afterwards pyroreaction 1-70 hour; Refrigerated separation gets carbon load binary metal alloy; Alloy is dispersed in to drip in the water alcohol mixed liquor contains the precious metal salt aqueous solution, added the strong reducing property solution reaction again 0.5-10 hour, can make carbon supported precious metal and modify the bianry alloy catalyst.
2. according to the said preparation method of claim 1, it is characterized in that noble metal comprises: platinum, rhodium, palladium, ruthenium, gold.
3. according to the said preparation method of claim 1, it is characterized in that bianry alloy comprises: palladium-copper alloy, palladium cobalt alloy, palladium ferroalloy, palladium-nickel alloy, Kufil, palladium manganese alloy, copper-cobalt alloy.
4. according to the said preparation method of claim 1, it is characterized in that carbon carrier comprises: graphite, carbon black, CNT, carbon fiber, fullerene, Graphene, conducting polymer and their mixture.
5. according to the said preparation method of claim 1, it is characterized in that used amino acid comprises: glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, aspartic acid, asparagine, glutamic acid, lysine, glutamine, methionine, serine, threonine, cysteine, proline, histidine, arginine.
6. according to the said preparation method of claim 1, it is characterized in that week reduction solution comprises: ethylene glycol, propane diols, glycerine, butanediol, pentanediol, glyoxal, MDA, butanedial, glutaraldehyde, ascorbic acid, citric acid, isoniazid.
7. according to the said preparation method of claim 1, it is characterized in that dilute alkaline soln comprises: NaOH, potassium hydroxide, lithium hydroxide, ammoniacal liquor, regulator solution pH value is 8-14.
8. according to the said preparation method of claim 1, it is characterized in that the water-heat process reaction temperature is 110～300 ℃, the reaction time is 1-70 hour.
9. according to the said preparation method of claim 1, it is characterized in that Pd2+ and its concentration of metal ions are 10～100mmol/L, the amino acid masses percentage concentration is 0.01%～4%.
10. according to the said preparation method of claim 1, it is characterized in that strong reducing property solution comprises: KBH
4, NaBH
4, N
2H
4
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| CN103272616A (en) * | 2013-06-07 | 2013-09-04 | 苏州诺信创新能源有限公司 | Proton exchange membrane fuel cell catalyst preparation method |
| CN103611946A (en) * | 2013-12-08 | 2014-03-05 | 福建医科大学 | Preparation method of gold nanocluster fluorescent materials protected by methionine |
| CN103908963A (en) * | 2013-01-04 | 2014-07-09 | 吉林师范大学 | Preparation method of high catalytic activity chemically reductive graphene-gold platinum palladium compound |
| CN104307524A (en) * | 2014-10-17 | 2015-01-28 | 南开大学 | Preparation method of Cu@Co nuclear shell nano-catalyst |
| CN104353467A (en) * | 2014-11-07 | 2015-02-18 | 湖南科技大学 | Trace palladium nanoparticle for electrochemical catalysis ethanol oxidation, preparation method and application of trace palladium nanoparticle |
| CN104415769A (en) * | 2013-09-05 | 2015-03-18 | 深圳先进技术研究院 | Cobalt-based/graphene compound catalyst as well as preparation method and application of cobalt-based/graphene compound catalyst |
| CN104415752A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | C3-fraction liquid phase selective hydrogenation catalyst as well as preparation method and application thereof |
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| CN104962774A (en) * | 2015-06-30 | 2015-10-07 | 贵州大学 | Super-structure Pd-Cu alloy and preparation method thereof |
| CN108636363A (en) * | 2018-05-25 | 2018-10-12 | 湖南大学 | The carbon nano tube compound material and its preparation method and application of glutamic acid modification |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014410A (en) * | 2004-08-27 | 2007-08-08 | 约翰逊马西有限公司 | Platinum alloy catalyst |
| EP1887642A1 (en) * | 2005-05-25 | 2008-02-13 | Nissan Motor Company Limited | Electrode material for fuel cell and fuel cell |
-
2011
- 2011-01-31 CN CN2011100352420A patent/CN102614891A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014410A (en) * | 2004-08-27 | 2007-08-08 | 约翰逊马西有限公司 | Platinum alloy catalyst |
| EP1887642A1 (en) * | 2005-05-25 | 2008-02-13 | Nissan Motor Company Limited | Electrode material for fuel cell and fuel cell |
Non-Patent Citations (2)
| Title |
|---|
| CHUANGANG HU ET AL.: "Preparation of high performance Pd catalysts supported on untreated multi-walled carbon nanotubes for formic acid oxidation", 《ELECTROCHIMICA ACTA》 * |
| RONGFANG WANG ET AL.: "Pt decorating PdCu/C as highly effective electrocatalysts for methanol oxidation", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
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Application publication date: 20120801 |