CN103540901A - Catalytic electrode composite thin film and preparation method thereof - Google Patents
Catalytic electrode composite thin film and preparation method thereof Download PDFInfo
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- CN103540901A CN103540901A CN201210246211.4A CN201210246211A CN103540901A CN 103540901 A CN103540901 A CN 103540901A CN 201210246211 A CN201210246211 A CN 201210246211A CN 103540901 A CN103540901 A CN 103540901A
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Abstract
The invention relates to a catalytic electrode material, and particularly provides a composite thin film of noble metals and carbon and a preparation method of the composite thin film. The composite thin film is characterized by being formed by nesting noble metal particles and carbon particles mutually, wherein the noble metals are platinum, iridium, ruthenium and rhodium; the carbon is amorphous carbon, diamond and/or diamond-like substances. The preparation method is characterized in that a closed deposition chamber is available, wherein negative bias is introduced to a workpiece and a target material; the deposition chamber is provided with an air inlet and an air outlet; a noble metal assembly is used as the target material; a conductive refractory material is used as the workpiece and is titanium alloy, niobium alloy, tungsten-molybdenum alloy, graphite or carbide. During preparation, the air pressure of the deposition chamber is 0.01-30 Pa, the voltage of the workpiece is minus 100 V to minus 300 V, the target material voltage is minus 600 V to minus 1,200 V, and the sputtering of the target material element is initiated to form plasma region sputtering deposition; then alkane gas is introduced at the flow rate of 10-60 sccm to deposit for 0.5-5 hours, so that a noble metal-carbon composite thin film can be obtained on the surface of the workpiece, and the thickness of the thin film is 100 nm to 50 mum.
Description
Technical field
The present invention relates to catalytic electrode material, a kind of precious metal and carbon compound film and preparation method thereof are provided especially.
Background technology
Noble coatings has good antioxidant property, electrocatalysis characteristic, stable chemical nature and erosion resistance, is the critical function material of supercoat and catalysis electrode.On refractory metal and alloy surface thereof, depositing noble metal can be brought into play the advantage of matrix itself and coating, overcomes its shortcoming.In < < Scripta Materials > > the 44th volume magazine of calendar year 2001 publication, < < Electrochemical properties of iridium-carbon nano composite films prepared by MOCVD > > mono-literary composition discloses and has utilized chemical vapour deposition technique to prepare iridium-carbon nano compound film, the method is used organic precursor method as deposition source, in vacuum moulding machine stove, by high temperature thermolysis, obtain noble coatings, but the thermally decomposed carbon impurity of lingering section.Residual carbon impurity can stop growing up of precious metal crystal grain, thereby causes iridium-carbon nano compound film.Utilize iridium-carbon nano compound film prepared by chemical vapour deposition technique to there is good catalysis and electrochemistry ability.In < < Platinum Metals Review > > the 49th volume magazine of publishing for 2005, < < Iridium/Carbon Films Prepared by MOCVD > > mono-literary composition discloses and has utilized chemical vapour deposition technique to prepare iridium-carbon film, the method utilizes praseodynium iridic compound as deposition source, pass into a small amount of oxygen and reduce the carbon content in iridium film, final iridium-carbon the film obtaining has good catalysis characteristics.The advantage of the method is that low temperature thermal decomposition obtains high temperature coating, obtains fine and close continuous coating, and the method shortcoming is that sedimentation rate is low to process parameter control difficulty, apparatus expensive, and equipment corrosion is serious, and maintenance cost is high.
Summary of the invention
The technical problem that the present invention will solve is to overcome the deficiencies in the prior art, and a kind of catalysis electrode laminated film is provided, and it is characterized in that this film forms by noble metal granule is mutually nested with carbon granule.In described laminated film, precious metal is for being platinum, iridium, ruthenium, rhodium.In described laminated film, your carbon is agraphitic carbon, diamond and/or quasi-diamond.
Another technical problem that the present invention will solve is to provide a kind of catalysis electrode preparation method of composite film, there is an airtight sediment chamber, workpiece and target lead to negative bias, there are an inlet mouth and an air outlet, it is characterized in that take that precious metal subassembly is as target, conducting refractory material is workpiece, and wherein conducting refractory material is titanium alloy, niobium alloy, miramint, graphite or carbide.Described inlet mouth gas is a kind of gas and the argon gas in methane, propane, propylene, and inlet mouth continues air inlet or pulsed air inlet; Air outlet continues to vacuumize or pulsed vacuumizes.Preparation process: regulate the distance between target and workpiece, vacuumize and make in sediment chamber the vacuum tightness vacuum that reaches capacity; Pass into argon gas to operating air pressure, sediment chamber's air pressure is 0.01 Pa-30 Pa again; Then slowly increase workpiece voltage, workpiece voltage is-100V～-300V, adjusts target voltage and workpiece voltage, and target voltage be-600V～-1200V to cause the sputter of target elements, formation plasma area sputtering sedimentation; Now pass into alkane gas, flow is 10sccm-60sccm again, deposition 0.5-5h, and workpiece surface can obtain precious metal-carbon compound film, and its thickness is 100nm～50 μ m.
Effect: the present invention compared with prior art, has the following advantages:
(1) cost is low;
(2) corrosion-free, pollution-free;
(3) sedimentation rate is very fast;
(4) compound coating has good catalysis and chemical property.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment is only not used in and limits the scope of the invention for the present invention is described, after having read the present invention, those skilled in the art all fall within the application's claims to the modification of the various equivalent form of values of the present invention and limit.
Embodiment
Embodiment 1
Use titanium alloy as workpiece, the highly purified platinum plate of take is target, in vacuum deposition chamber, from inlet mouth, passes into methane and argon gas methane flow is 20sccm, argon flow amount is 50sccm, operating air pressure 1Pa in vacuum chamber, target voltage is-900V that workpiece voltage is-200V.Through 2h deposition, can obtain platinum-carbon black look laminated film that about 8 μ m are thick.The compound laminated film of platinum-carbon is through projection electron microscopic observation, and laminated film is comprised of fine and close nano particle, and platinum grain is wrapped up by agraphitic carbon.Laminated film detects and shows that carbon content is 30at.%-25at.% through Electron Energy Disperse Spectroscopy.
Embodiment 2
Use graphite carbon as workpiece, the highly purified iridium dish of take is target, in vacuum deposition chamber, from inlet mouth, passes into propylene and argon gas propylene flow is 35sccm, argon flow amount is 40sccm, operating air pressure 5Pa in vacuum chamber, target voltage is-850V that workpiece voltage is-200V.Through 1h deposition, can obtain the thick iridium-carbon compound film of about 3 μ m.The compound laminated film sample of iridium-carbon and iridium coating layer sample carry out electro-chemical test, and sample goes out 1cm by AB rubber seal
2naked, before test, sample is respectively with alcohol and distilled water wiping and dry up, then immerse in the solution of 3.5%NaCl, test result shows that the compound laminated film sample of iridium-carbon has higher corrosion potential and lower current density than iridium coating layer sample, and the compound laminated film chemical property of iridium-carbon is better than the chemical property of iridium coating layer.
Above are only single embodiment of the present invention, but design concept of the present invention is not limited to this, allly utilizes this design to carry out the change of unsubstantiality to the present invention, all should belong to the behavior of invading the scope of protection of the invention.In every case be the content that does not depart from technical solution of the present invention, any type of simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (9)
1. a catalysis electrode laminated film, is characterized in that this film forms by noble metal granule is mutually nested with carbon granule.
2. according to the film described in claims 1, it is characterized in that described precious metal is platinum, iridium, ruthenium, rhodium.
3. according to the film described in claims 1, it is characterized in that described carbon is agraphitic carbon, diamond and/or quasi-diamond.
4. a preparation method for catalysis electrode laminated film, has an airtight sediment chamber, and workpiece and target lead to negative bias, there are an inlet mouth and an air outlet, it is characterized in that take that precious metal subassembly is as target, conducting refractory material is workpiece, and sediment chamber's air pressure is 0.01Pa-30Pa.
5. according to the preparation method described in claims 4, it is characterized in that workpiece voltage-100V～-300V, target voltage is-600V～-1200V.
6. according to the preparation method described in claims 4, it is characterized in that inlet mouth gas is a kind of gas and the argon gas in methane, propane, propylene, alkane gas flow is 10sccm-60sccm, and inlet mouth continues air inlet or pulsed air inlet.
7. according to the preparation method described in claims 4, it is characterized in that air outlet continues to vacuumize or pulsed vacuumizes.
8. according to the preparation method described in claims 4, it is characterized in that film thickness is 100nm～50 μ m, depositing time is 0.5-5h.
9. according to the preparation method described in claims 4, it is characterized in that described conducting refractory material is titanium alloy, niobium alloy, miramint, graphite or carbide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210246211.4A CN103540901A (en) | 2012-07-16 | 2012-07-16 | Catalytic electrode composite thin film and preparation method thereof |
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| CN201210246211.4A CN103540901A (en) | 2012-07-16 | 2012-07-16 | Catalytic electrode composite thin film and preparation method thereof |
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| CN103540901A true CN103540901A (en) | 2014-01-29 |
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| CN201210246211.4A Pending CN103540901A (en) | 2012-07-16 | 2012-07-16 | Catalytic electrode composite thin film and preparation method thereof |
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Citations (8)
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| CN1346902A (en) * | 2001-09-28 | 2002-05-01 | 太原理工大学 | Plasma co-diffusion process of metal and non-metal elements |
| CN1719648A (en) * | 2004-07-08 | 2006-01-11 | 三星Sdi株式会社 | Supported catalyst and fuel cell using the same |
| US20060115712A1 (en) * | 2004-11-26 | 2006-06-01 | Hee-Tak Kim | Electrode for fuel cell, fuel cell system comprising the same, and method for preparing the same. |
| CN1957116A (en) * | 2004-05-27 | 2007-05-02 | 凸版印刷株式会社 | Nanocrystal diamond film, process for producing the same and apparatus using nanocrystal diamond film |
| JP2007268360A (en) * | 2006-03-30 | 2007-10-18 | Osaka Prefecture | Catalyst and its manufacturing method |
| CN101515648A (en) * | 2009-03-19 | 2009-08-26 | 同济大学 | Novel membrane electrode component available for fuel cell, preparation method and application thereof |
| CN101740787A (en) * | 2009-12-29 | 2010-06-16 | 浙江理工大学 | Metal particle-amorphous diamond composite anode for fuel cell and preparation method thereof |
| CN102484255A (en) * | 2009-06-29 | 2012-05-30 | 株式会社爱考斯研究 | Reaction layer for fuel cell |
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2012
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346902A (en) * | 2001-09-28 | 2002-05-01 | 太原理工大学 | Plasma co-diffusion process of metal and non-metal elements |
| CN1957116A (en) * | 2004-05-27 | 2007-05-02 | 凸版印刷株式会社 | Nanocrystal diamond film, process for producing the same and apparatus using nanocrystal diamond film |
| CN1719648A (en) * | 2004-07-08 | 2006-01-11 | 三星Sdi株式会社 | Supported catalyst and fuel cell using the same |
| US20060115712A1 (en) * | 2004-11-26 | 2006-06-01 | Hee-Tak Kim | Electrode for fuel cell, fuel cell system comprising the same, and method for preparing the same. |
| JP2007268360A (en) * | 2006-03-30 | 2007-10-18 | Osaka Prefecture | Catalyst and its manufacturing method |
| CN101515648A (en) * | 2009-03-19 | 2009-08-26 | 同济大学 | Novel membrane electrode component available for fuel cell, preparation method and application thereof |
| CN102484255A (en) * | 2009-06-29 | 2012-05-30 | 株式会社爱考斯研究 | Reaction layer for fuel cell |
| CN101740787A (en) * | 2009-12-29 | 2010-06-16 | 浙江理工大学 | Metal particle-amorphous diamond composite anode for fuel cell and preparation method thereof |
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| 廖代伟等: "《催化科学导论》", 31 May 2006, 化学工业出版社教材出版中心 * |
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Application publication date: 20140129 |