CN100588459C - Reverse micelle method for preparing platinum ruthenium/carbon catalyst - Google Patents
Reverse micelle method for preparing platinum ruthenium/carbon catalyst Download PDFInfo
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- CN100588459C CN100588459C CN200710060188A CN200710060188A CN100588459C CN 100588459 C CN100588459 C CN 100588459C CN 200710060188 A CN200710060188 A CN 200710060188A CN 200710060188 A CN200710060188 A CN 200710060188A CN 100588459 C CN100588459 C CN 100588459C
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Abstract
The invention discloses a reverse micelles method of preparing platinum ruthenium/carbon catalyst, which includes the following steps: 0.02 to 0.10mol/L chloroplatinic acid aqueous solution and 0.04 to 0.20 mol/L ruthenium trichloride aqueous solution are prepared to form water phase; hexamethylene is prepared into oil phase, sodium laurylsulfate is taken as surfactant and n-octyl alcohol is takenas cosurfactant; the mass ratio of sodium laurylsulfate, hexamethylene and n-octyl alcohol is 1:0.07 to 0.15:0.5 to 1.2; the product is mixed and added in carbon black, and the receives ultrasonic vibration and mechanical mixing for 20 to 60 min, so that a reverse micelle is loaded on the carbon black; a reducing agent, demulsifier acetone and solution are added for filtration and drying. The reverse micelle of the invention provides a micro environment, and can become an ideal place of nano particle synthetization. Because of the method of preparing nano particles, only simple equipments areneeded, the operation is under room temperature, the metal particles have grain size which is easy to be controlled and spread quite evenly.
Description
Technical field
The present invention relates to the Proton Exchange Membrane Fuel Cells technical field, also can be widely used in other chemical field.The present invention be more particularly directed to a kind of preparation carbon and carry the reverse micelle method of platinum ruthenium (PtRu/C) catalyst.
Background technology
Fuel cell is a kind of efficient, eco-friendly TRT, and the chemical energy that it directly will be stored in fuel and the oxidant is converted into electric energy.In today that environment and the energy receive much concern, the research and development of fuel cell more and more are subjected to the attention of national governments.
Proton Exchange Membrane Fuel Cells (PEMFC) has the energy conversion efficiency height, and specific energy is big, start rapidly and series of advantages such as environmental friendliness, and be following most effective and one of the generation technology that cleans most.Membrane electrode (Membrane﹠amp; Electrode Assembly is the parts of PEMFC most critical MEA), is the core that the PEMFC electrochemical reaction can efficiently be carried out, and membrane electrode is made up of diffusion layer, catalyst layer and PEM usually.Eelctro-catalyst adopts load type platinum/carbon (Pt/C) or platinum-ruthenium/carbon (Pt-Ru/C), and wherein the Pt-Ru/C catalyst also is the first-selected eelctro-catalyst of DMFC (DMFC).The general perfluorinated sulfonic acid type PEM (as the Nafion series membranes of du pont company) that adopts of PEM with high proton conductivity.
Eelctro-catalyst is to make among the PEMFC fuel and oxidant finish oxidation and reduction reaction conditio sune qua non respectively.Precious metals pt is the highest and stable catalyst to the reduction reaction activity of the oxidation reaction of hydrogen and oxygen up to now, so the first-selected Pt of PEMFC catalyst is catalyst based.But, adopt the PEMFC of the hydrogen of natural gas or liquid fuel reformation generation to exist Pt to cause the problem of power decline because of CO poisons.The eelctro-catalyst that exploitation has good resistance CO poisoning performance is to address this problem important method.The PtRu eelctro-catalyst is considered to one of best anti-CO poisoned catalyst at present.Studies show that in the Pt-Ru/C catalyst, the electronic section on the Ru atom is transferred on the Pt atom, thereby make it show the concerted catalysis effect.And Ru can make water decomposition form the oxygenated species (OH) of ADSORPTION STATE
Ads, (OH)
AdsCan oxidation be adsorbed on the CO toxin on the catalytic active site, make catalyst possess certain tolerance limit ability CO
Prepare highly active PtRu/C catalyst and be always the hot subject of PEMFC in recent years.At present the more Pt-Ru/C Preparation of catalysts method of report has inorganic colloid method, infusion process, gel sol method and the precipitation method etc., and there is the particle bad dispersibility in the catalyst of these original methods preparations, and the inhomogeneous and reaction condition of particle diameter is problem such as harshness relatively.Because Preparation of catalysts technology determines its The Nomenclature Composition and Structure of Complexes, and then influences its performance (comprising activity, life-span and utilization rate etc.), research PtRu/C Preparation of catalysts method and technology are extremely important.
Summary of the invention
The present invention proposes a kind of inverse micelle method for preparing platinum ruthenium/carbon catalyst, and step is as follows:
1) the configuration concentration scope is 0.02～0.10mol/L chloroplatinic acid aqueous solution, and the configuration concentration scope is 0.04～0.20mol/L ruthenium trichloride aqueous solution, and two kinds of solution constitute water jointly;
2) cyclohexane is an oil phase, and lauryl sodium sulfate is a surfactant, and n-octyl alcohol is a cosurfactant; The mass ratio of lauryl sodium sulfate and cyclohexane and n-octyl alcohol is 0.07～0.15: 0.5～1.2;
3) above-mentioned steps 2) sonic oscillation or mechanical agitation 15～40 minutes, drip the step 1) water then continuously, the mol ratio of water and surfactant should be 4～11; Ultrasonic concussion 20～60 minutes forms transparent reverse micelle system;
4) in above-mentioned steps 3) add carbon black in the described system, ultrasonic concussion or mechanical agitation 20～60 minutes load on the carbon black reverse micelle;
5) in above-mentioned steps 4) add reducing agent in the described system, reacted 20～40 minutes under mechanical agitation or the ultrasonic oscillation condition, continued stirring reaction 1～2 hour; Reducing agent adopts potassium borohydride or sodium borohydride aqueous solution, and consumption is 3～15 times of theoretical value, and volume is 3) 0.5 ~ 2 times of described water volume;
6) stir or the ultrasonic oscillation condition under add demulsifier acetone or absolute ethyl alcohol, addition is to leave standstill behind 25%～40%, 20～40 minutes of cyclohexane volume, to system layering;
7) solution filters, and with the ethanol water washing, spends deionised water again;
8) drying under nitrogen protection, or direct 50 ℃～90 ℃ vacuum drying 2～6 hours.
The present invention adopts reverse micelle method to prepare the PtRu/C catalyst, and this PtRu/C catalyst has high electro catalytic activity to hydrogen and oxygen, methyl alcohol and the oxygen electrochemical reaction of carrying out in the fuel cell especially.Prepared PtRu/C catalyst has that metal carrying capacity height, particle diameter are little, the characteristics of good dispersion and even particle size distribution.As Fig. 1 and Fig. 2 is that (black particles is the PtRu alloying pellet to transmission electron microscope on the photo for Transmission Electron Microscope, the design sketch according to the PtRu/C catalyst of the present invention's preparation that TEM) characterizes.Instrument adopts TECNAIG2F-20 type field, Dutch Philip transmission electron microscope.The PtRu/C catalyst (Fig. 1 and Fig. 2) of the present invention's preparation is measured through energy dispersive spectroscopy (EDS), and the total content of Pt and Ru is respectively 19.4% and 29.65% mass fraction, and the atomic ratio of Pt and Ru was respectively 1: 0.94 and 1: 0.95.Reverse micelle (that is water-in-oil microemulsion) provides a kind of microenvironment, can become the synthetic place (also being called little " reactor ") of desirable nano particle, adopt this method to prepare nano particle, equipment is simple, ambient operation, the metallic particles particle diameter is controlled easily and is distributed more even.
Description of drawings
Fig. 1: embodiment 1PtRu/C catalyst transmission electron microscope picture;
Fig. 2: embodiment 2PtRu/C catalyst transmission electron microscope picture.
The specific embodiment
Embodiment 1
1. dispose chloroplatinic acid (H
2PtCl
6) aqueous solution, its concentration is 0.0386mol/L; Configuration ruthenium trichloride (RuCl
3) aqueous solution, its concentration 0.0765mol/L.
2. dispose cyclohexane, lauryl sodium sulfate and n-octyl alcohol mixed liquor.The mass ratio of lauryl sodium sulfate and cyclohexane is 0.115, with the mass ratio of n-octyl alcohol be 0.7.
3. get 2. mixed liquor 100ml of above-mentioned steps, the mol ratio of water and surfactant is 7, and sonic oscillation 20 minutes drips the 2.19ml chloroplatinic acid and the 1.1ml ruthenium trichloride aqueous solution then respectively.Ultrasonic concussion 30 minutes forms transparent reverse micelle system.
4. in the 3. described system of above-mentioned steps, add carbon black 100mg Vulcan xC-72 carbon black, ultrasonic concussion 20 minutes.
5. add 0.2mol/L potassium borohydride aqueous solution 4.5ml (6 times of theoretical value, water volume 2 times) in the 4. described system of above-mentioned steps, reaction is 20 minutes under the ultrasonic concussion condition, continues to stir to continue reaction 2 hours.
6. add 30ml acetone breakdown of emulsion, ultrasonic oscillation 30 minutes leaves standstill to system layering.
7. solution filters, and uses the absolute ethyl alcohol solution washing, spends deionised water again.
8. 60 ℃ of vacuum drying are 3 hours.
Implementation result is seen accompanying drawing 1.Energy dispersive spectroscopy (EDS) is measured, PtRu total content 19.4% in the catalyst, the atomic ratio of Pt and Ru 1: 0.94.
Embodiment 2
1. dispose chloroplatinic acid (H
2PtCl
6) aqueous solution, its concentration is 0.1mol/L; Configuration ruthenium trichloride (RuCl
3) aqueous solution, its concentration is 0.04mol/L.
2. dispose cyclohexane, lauryl sodium sulfate and n-octyl alcohol mixed liquor.The mass ratio of lauryl sodium sulfate and cyclohexane is 0.078, with the mass ratio of n-octyl alcohol be 1.0.
3. get 2. mixed liquor 130ml of above-mentioned steps, the mol ratio of water and surfactant is 11, and sonic oscillation 15 minutes drips the 1.45ml chloroplatinic acid and the 3.61ml ruthenium trichloride aqueous solution then respectively.Ultrasonic concussion 60 minutes forms transparent reverse micelle system.
4. in the 3. described system of above-mentioned steps, add carbon black 100mg Vulcan XC-72 carbon black, ultrasonic concussion 30 minutes.
5. add 1.5mol/L sodium borohydride aqueous solution 2.53ml (15 times of theoretical value, water volume 0.5 times) in the 4. described system of above-mentioned steps, reaction is 40 minutes under the ultrasonic concussion condition, and mechanical agitation continues reaction 1 hour.
6. add 48ml acetone breakdown of emulsion, ultrasonic oscillation 40 minutes leaves standstill to system layering.
7. solution filters, and with the ethanol water washing, spends deionised water again.
8. 90 ℃ of vacuum drying are 2 hours.
Implementation result is seen accompanying drawing 2.Measure through energy dispersive spectroscopy (EDS), the total content of Pt and Ru is 29.65% mass fraction, and the atomic ratio of Pt and Ru was respectively 1: 0.95.
Embodiment 3
1. dispose chloroplatinic acid (H
2PtCl
6) aqueous solution, its concentration is 0.02mol/L; Configuration ruthenium trichloride (RuCl
3) aqueous solution, its concentration range is 0.20mol/L.
2. dispose cyclohexane, lauryl sodium sulfate and n-octyl alcohol mixed liquor.The mass ratio of lauryl sodium sulfate and cyclohexane is 0.15, with the mass ratio of n-octyl alcohol be 1.2.
3. get 2. mixed liquor 150ml of above-mentioned steps, the mol ratio of water and surfactant is 4.2, and sonic oscillation 40 minutes is distinguished the Dropwise 5 .10ml chloroplatinic acid and the 0.25ml ruthenium trichloride aqueous solution then.Ultrasonic concussion 20 minutes forms transparent reverse micelle system.
4. in the 3. described system of above-mentioned steps, add carbon black 100mg Vulcan xC-72 carbon black, ultrasonic concussion 60 minutes.
5. in the 4. described system of above-mentioned steps, add 0.053mol/L potassium borohydride aqueous solution 8.0ml (3 times of theoretical value, water volume 1.5 times), mechanical agitation successive reaction 1 hour 40 minutes.
6. add 45ml absolute ethyl alcohol breakdown of emulsion, ultrasonic oscillation 20 minutes leaves standstill to system layering.
7. solution filters, and with the ethanol water washing, spends deionised water again.
8. 50 ℃ of vacuum drying are 6 hours.
Implementation result is seen accompanying drawing 2.Measure through energy dispersive spectroscopy (EDS), the total content of Pt and Ru is 19.2% mass fraction, and the atomic ratio of Pt and Ru was respectively 2: 0.91.
The present invention's preparation carbon open and that disclose carries the reverse micelle method of platinum ruthenium (PtRu/C) catalyst, can be by using for reference this paper disclosure.Although method of the present invention is described by preferred embodiment, but those skilled in the art obviously can change method as herein described in not breaking away from content of the present invention, spirit and scope, more particularly, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (1)
1. inverse micelle method for preparing platinum ruthenium/carbon catalyst is characterized in that step is as follows:
1) the configuration concentration scope is 0.02～0.10mol/L chloroplatinic acid aqueous solution, and the configuration concentration scope is 0.04～0.20mol/L ruthenium trichloride aqueous solution, and two kinds of solution constitute water jointly;
2) cyclohexane is an oil phase, and lauryl sodium sulfate is a surfactant, and n-octyl alcohol is a cosurfactant; The mass ratio of lauryl sodium sulfate and cyclohexane and n-octyl alcohol is respectively 0.07～0.15 and 0.5～1.2;
3) above-mentioned steps 2) sonic oscillation or mechanical agitation 15～40 minutes, drip the step 1) water then continuously, the mol ratio of water and surfactant should be 4～11; Ultrasonic concussion 20～60 minutes forms transparent reverse micelle system;
4) in above-mentioned steps 3) add carbon black in the described system, ultrasonic concussion or mechanical agitation 20～60 minutes load on the carbon black reverse micelle;
5) in above-mentioned steps 4) add reducing agent in the described system, reacted 20～40 minutes under mechanical agitation or the ultrasonic oscillation condition, continued stirring reaction 1～2 hour; Reducing agent adopts potassium borohydride or sodium borohydride aqueous solution, and consumption is 3～15 times of theoretical value, and volume is 0.5～2 times of step 3) water volume;
6) stir or the ultrasonic oscillation condition under to add acetone be demulsifier, addition is to leave standstill behind 25%～40%, 20～40 minutes of cyclohexane volume, to system layering;
7) solution filters, and with the ethanol water washing, spends deionised water again;
8) drying under nitrogen protection, or direct 50 ℃～90 ℃ vacuum drying 2～6 hours.
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| EP4104926A4 (en) * | 2020-02-10 | 2023-08-09 | University of Yamanashi | Supported metal catalyst, method for producing same, and method for producing carrier |
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| JP5715264B2 (en) * | 2010-12-29 | 2015-05-07 | オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー | Preparation of platinum-ruthenium nanoalloy / graphene catalyst |
| US20130252138A1 (en) * | 2010-12-29 | 2013-09-26 | Ocean's King Lighting Science & Technology Co.,Ltd | Pt/graphene catalyst, preparation method and use thereof |
| CN102989450B (en) * | 2012-12-03 | 2015-03-11 | 中国科学院大连化学物理研究所 | Preparation method, structural feature and application of carrying type nanometer electrocatalyst |
| CN113070059A (en) * | 2021-03-25 | 2021-07-06 | 湘潭银河新能源有限公司 | Preparation method of platinum-based composite nano electrode catalyst |
| CN114749172B (en) * | 2022-04-21 | 2023-06-27 | 清华大学 | Continuous preparation method of carbon nanomaterial loaded with small-particle-size noble metal |
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Non-Patent Citations (6)
| Title |
|---|
| A new supported catalyst for methanol oxidation prepared bya reverse micelles method. Yicheng Liu, et al.Electrochemistry Communication,Vol.4 . 2002 |
| A new supported catalyst for methanol oxidation prepared bya reverse micelles method. Yicheng Liu,et al.Electrochemistry Communication,Vol.4. 2002 * |
| A review of anode catalysis in the direct methanol fuel cell. Hansan Liu, et al.Journal of Power Sources,Vol.155 . 2006 |
| A review of anode catalysis in the direct methanol fuel cell. Hansan Liu,et al.Journal of Power Sources,Vol.155. 2006 * |
| Catalytic activity of Pt-Ru alloys synthesized by amicroemulsion method in direct methanol fuel cells. L. Xiong, A. Manthiram.Solid State Ionic,Vol.176 . 2005 |
| Catalytic activity of Pt-Ru alloys synthesized by amicroemulsion method in direct methanol fuel cells.L.Xiong,A.Manthiram.Solid State Ionic,Vol.176. 2005 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP4104926A4 (en) * | 2020-02-10 | 2023-08-09 | University of Yamanashi | Supported metal catalyst, method for producing same, and method for producing carrier |
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