CN101683614A - Ethanol oxidation catalyst, manufacturing method thereof and fuel cell using same - Google Patents
Ethanol oxidation catalyst, manufacturing method thereof and fuel cell using same Download PDFInfo
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- CN101683614A CN101683614A CN200810173761A CN200810173761A CN101683614A CN 101683614 A CN101683614 A CN 101683614A CN 200810173761 A CN200810173761 A CN 200810173761A CN 200810173761 A CN200810173761 A CN 200810173761A CN 101683614 A CN101683614 A CN 101683614A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides an ethanol oxidation catalyst containing Pt/Ru alloy and stannic oxide, a manufacturing method thereof, a fuel battery electrode containing the ethanol oxidation catalyst, and afuel cell using the electrode with excellent discharge efficiency.
Description
Technical field
The fuel cell that the present invention relates to a kind of ethanol oxidation catalyst, its manufacture method and use this ethanol oxidation catalyst.
The background technology fuel cell decomposes chemistry of fuel and the chemical energy of fuel is directly changed into electric energy.Therefore, fuel cell is useful in various industrial circles.In this respect, carried out about using the research of methyl alcohol as the direct fuel in the low-temperature fuel cell.
In DMFC (DMFC), use Pt-Ru bianry alloy catalyst to be adsorbed onto on the Pt to be suppressed at the carbon monoxide that produces in the methanol oxidation process.
Yet, because methyl alcohol is harmful, the fuel that therefore needs a kind of alternative methyl alcohol of exploitation to use.Therefore, attempted the method for the harmless ethanol instead of methanol of multiple use.
Disclose the Pt-Ru bianry alloy catalyst that is used for methanol oxidation, the catalyst (JP 2004-152748A) that perhaps comprises a kind of and Pt among W, Sn, Mo, Cu, Au, Mn and the V is as ethanol oxidation catalyst.
Yet these catalyst do not have enough activity for oxidation of ethanol, therefore need to improve the activity of oxidation of ethanol.
Summary of the invention
The invention provides a kind of have ethanol oxidation catalyst, its manufacture method of excellent oxidation of ethanol ability, the direct alcohol fuel cell that comprises the fuel cell electrode of this ethanol oxidation catalyst and comprise this electrode.
According to an aspect of the present invention, ethanol oxidation catalyst comprises Pt/Ru alloy and tin oxide, and wherein the mol ratio of Pt/Ru alloy oxidation tin is 2.5-3.5: 1.
According to a further aspect in the invention, provide a kind of method of making ethanol oxidation catalyst, this method comprises:
By preparing Pt precursor and Ru precursor and Sn precursor and respectively described precursor is dissolved in first solvent separately, and mix the solution of described precursor and prepare metal salt solution;
By catalyst carrier and solvent are prepared carrier solution;
Prepare loaded catalyst by pH with supported catalyst particles on catalyst carrier with metal salt solution and carrier solution mixing and adjusting mixture;
Carry out the heat treatment process first time by heat treatment gains under the about 70 ℃ temperature of about 50-;
Carry out the heat treatment process second time by heat treatment gains under the about 160 ℃ temperature of about 125-;
Regulate the pH value of gains; With
Separation is also washed this loaded catalyst.
Description of drawings
Above-mentioned and further feature of the present invention and advantage will be described its illustrative embodiments in detail by the reference accompanying drawing and become distincter, in the accompanying drawings:
Fig. 1 is the flow chart of explanation manufacturing according to the process of the ethanol oxidation catalyst of embodiment of the present invention;
Fig. 2 is the figure of explanation according to the X-ray diffraction pattern (XRD) of the Pt/Ru alloy loaded catalyst of embodiment 1 and Comparative Examples 2 preparations;
Fig. 3 is explanation according to the cell voltage of the fuel cell of preparation example 1 and comparative preparation example 1 preparation and the power density figure with respect to current density.
The specific embodiment
Hereinafter, the present invention is described more fully with reference to the accompanying drawings, illustrative embodiments of the present invention shown in the drawings.
Ethanol oxidation catalyst according to embodiment of the present invention comprises Pt/Ru alloy and tin oxide.
Pt and Ru can be 2.5-3.5 to the mol ratio of tin oxide in the ethanol oxidation catalyst: 1, and preferred 2.9-3.1: 1, and more preferably 3.0: 1.If Pt and Ru to the mol ratio of tin oxide less than 2.5: 1, the then initial oxidation reaction reduction of ethanol.On the other hand, if Pt and Ru to the mol ratio of tin oxide greater than 3.5: 1, then the intermediate that produces of oxidation can not fully be removed.
In ethanol oxidation catalyst, the mol ratio of Pt and Ru can be 3-15: 1, and preferred 4-14: 1.
If the mol ratio of Pt and Ru was greater than 15: 1, then the oxidability of ethanol can reduce.On the other hand, if the mol ratio of Pt and Ru less than 3: 1, then is difficult to remove CO.
Ethanol oxidation catalyst can further comprise the carrier of supporting Pt on it/Ru alloy and tin oxide.In the ethanol oxidation catalyst of 100 weight portions, the amount of carrier can be about 90 weight portions of about 50-.
Hereinafter, with reference to Fig. 1 the method for manufacturing according to the ethanol oxidation catalyst of embodiment of the present invention described.
At first, respectively Pt precursor and Ru precursor and Sn precursor are dissolved in first solvent.
The quantitative mol ratio between Pt precursor, Ru precursor and the Sn precursor makes that being included in Pt in the final ethanol oxidation catalyst and Ru is 2.5-3.5 to the mol ratio of Sn: 1.If the mol ratio between Pt precursor, Ru precursor and the Sn precursor not within above-mentioned scope, then can not get the expectation ratio of each component in final loaded catalyst.
In addition, first solvent can be water or polyalcohol.Water can be deionized water, and polyalcohol can be ethylene glycol, triethylene glycol etc.Each of Pt precursor, Ru precursor and Sn precursor can be dissolved in the polyalcohol.
Be dissolving Pt precursor, in the Pt precursor of 100 weight portions, the amount of first solvent can be about 9000 weight portions of about 3000-.Be dissolving Ru precursor, in the Ru precursor of 100 weight portions, the amount of first solvent can be about 26000 weight portions of about 7000-.Be dissolving Sn precursor, in the Sn precursor of 100 weight portions, the amount of first solvent can be about 15000 weight portions of about 4000-.
The Pt precursor can be the salt that dissociates easily in water, for example chlorination Pt, sulfuric acid Pt or nitric acid Pt, and the Ru precursor also can be the salt that dissociates easily in water, for example chlorination Ru, sulfuric acid Ru or nitric acid Ru.
In addition, the Sn precursor can be SnCl
45H
2O, SnCl
22H
2O, Sn (C
2H
5O)
4, K
2SnO
3Deng.
Pt precursor, Ru precursor and Sn precursor are dissolved in respectively in first solvent to form Pt precursor solution, Ru precursor solution and Sn precursor solution, then described precursor solution are mixed with the preparation metal salt solution.
The catalyst carrier of load active component is dispersed in second solvent with the preparation carrier solution.Catalyst carrier can be carbonaceous carrier, zeolite, silica/alumina etc., and preferred carbonaceous carrier or zeolite.
The carbonaceous carrier can be graphite, carbon dust, acetylene black, carbon black, activated carbon, mesoporous carbon, CNT, carbon nano-fiber, carbon nanohorn (nanohorn), carbon nano ring, carbon nanocoils, fullerene (C
60) etc.
Second solvent that is used for the dispersed catalyst carrier can be ethylene glycol, water, triethylene glycol etc.
Then metal salt solution and carrier solution are mixed, and use the pH conditioning agent that the pH of mixture is adjusted to 10-14.The pH conditioning agent can be aqueous slkali, for example NaOH, NH
4OH, KOH, Ca (OH)
2Deng.
If the pH of mixture is lower than above-mentioned scope, then the amount of Hai Yuan Pt, Sn and Ru reduces.Therefore, the amount that loads on supported catalyst reduces, and the cohesion of the catalyst of load.If the pH of mixture is higher than above-mentioned scope, then the particle diameter of catalyst can increase.
Use is under the about 70 ℃ temperature of about 50-, and the mixture of the adjusted pH of the heat treatment process heat treatment first time under about 60 ℃ especially.Mixture can 3-7 ℃/min the rate of heat addition heat-treat.If the temperature during first time heat treatment process is less than 50 ℃, then reduction reaction is not fully carried out.On the other hand, if the temperature during first time heat treatment process greater than 70 ℃, then particle can be grown, and makes the catalyst particle size skewness thus.If the rate of heat addition is less than above-mentioned scope, then reaction rate reduces, so nucleation is carried out unevenly.If the rate of heat addition is greater than above-mentioned scope, then reaction rate increases, and therefore, particle size distribution is even like that not as expectation.
After carrying out the heat treatment process first time as mentioned above, under the about 160 ℃ temperature of about 125-, and preferably under about 140 ℃, carry out the heat treatment process second time.The rate of heat addition during the heat treatment process can be about 3-7 ℃/min for the second time.
If the temperature of heat treatment process is lower than 125 ℃ for the second time, then reduction reaction is not fully carried out.If the temperature of heat treatment process is higher than 160 ℃ for the second time, then particle size increases too many.If the rate of heat addition is less than above-mentioned scope, then particle size increases too many.If the rate of heat addition is greater than above-mentioned scope, then particle is grown unevenly, and therefore the particle size distribution of catalyst may be inhomogeneous.
Reduction reaction is carried out under the temperature of the heat treatment process second time.
Then, use acid solution for example HCl solution the pH of mixture is adjusted to 1-5.If the pH of mixture is less than 1, then the alloy of Xing Chenging can be dissolved in the mixture owing to high acidity.If the pH of mixture is greater than 5, then the interaction between catalyst granules and the carrier reduces, and therefore catalyst granules is not to load on fully on the carrier but stay in the solution.
Use conventional method for example to filter and centrifugal next separating obtained thing, wash then to prepare ethanol oxidation catalyst of the present invention.
According to above-mentioned in polyalcohol the method for dissolving precursor and the method for two phase heat treatment, can prepare and have the ethanol oxidation catalyst that is carried on the catalyst granules that comprises Pt/Ru alloy and tin oxide on the carrier.This ethanol oxidation catalyst has the activity of the promotion oxidation of ethanol of increase, even and when a large amount of metal of load on the carrier, ethanol oxidation catalyst also has excellent dispersiveness.
In addition, in the ethanol oxidation catalyst of 100 weight portions, the gross weight of Pt/Ru alloy and tin oxide can be about 90 parts of about 50-.If in the ethanol oxidation catalyst of 100 weight portions, the gross weight of Pt/Ru alloy and tin oxide then use the thickness of the anode catalyst layer of ethanol oxidation catalyst preparation to increase, so resistance is too high less than 50 weight portions.If in the ethanol oxidation catalyst of 100 weight portions, the gross weight of Pt/Ru alloy and tin oxide is greater than 90 weight portions, and then the particle diameter of catalyst is greater than 10nm or particle aggregation, and therefore specific area reduces.
The carrier of supporting Pt/Ru alloy and tin oxide can be carbonaceous carrier, zeolite, silica/alumina etc., and preferred carbonaceous carrier or zeolite.The carbonaceous carrier can be graphite, carbon dust, acetylene black, carbon black, activated carbon, mesoporous carbon, CNT, carbon nano-fiber, carbon nanohorn, carbon nano ring, carbon nanocoils, fullerene (C
60) etc.In ethanol oxidation catalyst according to the present invention, when irradiation has 1.541
During the Cu K α X-ray of wavelength, locate to observe diffraction maximum corresponding to the Pt/Ru alloy at the Bragg angle (2 θ) of 35-50 degree.Diffraction maximum can derive from Pt (111) face and Pt (200) face of ethanol oxidation catalyst.
Observe corresponding to SnO at about 34 degree and about 52 degree places
2Main diffraction maximum.Therefore, can find out the SnO of Pt/Ru alloy and nano-scale
2Intensive dispersion and coexistence.
Use the Cu K α X-ray analysis X-ray diffraction character that under 45kV, 40mA, produces by diffractometer (Shimadzu model XRD-6000).
In addition, the quantitative analysis of Pt/Ru alloy in the ethanol oxidation catalyst and tin oxide can be undertaken by inductively coupled plasma (ICP).
Simultaneously, use the ethanol oxidation catalyst of manufacturing method according to the invention preparation to can be used as the active component of the oxidation of ethanol of (especially in the anode electrode) ethanol in the electrode that promotes fuel cell, and can use conventional method to be used for the electrode of fuel cell.
Ethanol oxidation catalyst with dispersant such as isopropyl alcohol, tert-butyl acetate and n-butyl acetate, and ionomer such as Nafion disperse with the preparation slurry.Then slurry is coated on the gas diffusion layers.
Gas diffusion layers comprises carrier substrates and carbon-coating.
Carbon-coating can followingly form: with carbon black and solvent for example isopropyl alcohol and adhesive for example polytetrafluoroethylene (PTFE) mix, and this mixture is coated on the carrier substrates.Then, dry and heat treatment gains.
Carrier substrates can be carbon paper, preferred waterproof carbon paper, and more preferably be coated with the waterproof silica aerogel layer the waterproof carbon paper, or charcoal cloth.
The hydrophobic polymer that the waterproof carbon paper can comprise about 50% weight of about 5%-is for example PTFE, and this hydrophobic polymer can be clinkering.With gas diffusion layers be processed into waterproof with guarantee polar liquid reactant and gas reactant advance/go out passage.
In having the waterproof carbon paper of waterproof silica aerogel layer, the waterproof silica aerogel layer contains carbon black and as the hydrophobic polymer of the about 50 weight % of about 20-of hydrophobic adhesive PTFE for example.The waterproof silica aerogel layer is applied to waterproof carbon paper side.Hydrophobic polymer in the waterproof silica aerogel layer is clinkering.
In addition, the fuel cell according to embodiment of the present invention can comprise: the negative electrode that comprises catalyst layer and gas diffusion layers; The anode that comprises catalyst layer and gas diffusion layers; And the dielectric film between negative electrode and anode, wherein at least one of negative electrode and anode (especially anode) can comprise ethanol oxidation catalyst prepared in accordance with the present invention.
This fuel cell can be used for direct alcohol fuel cell (DEFC).
This fuel cell can use the method that is generally used for making fuel cell to prepare, and this method will not describe in detail in this article.
According to the embodiment of the present invention, this fuel cell is the direct alcohol fuel cell that has with the DMFC same structure.
According to the present invention, provide a kind of have ethanol oxidation catalyst, its manufacture method of excellent alcohol oxidation activity, the fuel cell that comprises the fuel cell electrode of this ethanol oxidation catalyst and use this electrode with excellent generating efficiency.
Now with reference to following examples the present invention is described in more detail.Following examples only are used for the illustrative purpose and are not intended to limit the scope of the invention.
Embodiment 1: the preparation of ethanol oxidation catalyst
With H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2O is dissolved in the 50ml ethylene glycol fully, stirs simultaneously with the preparation metal salt solution.Regulate H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio of Pt, Sn and Ru is 2.6: 1: 0.4 in the catalyst of final preparation.
0.370g carbon black carrier is dispersed in the 100ml ethylene glycol, stirs homogeneous dispersion simultaneously with preparation catalyst carrier solution.
Prepared catalyst carrier solution is joined in the metal salt solution, and use NaOH solution that the pH of mixture is adjusted to 13.
Gains used oil bath to be heated to 60 ℃ for the first time in 30 minutes, were heated to 140 ℃ for the second time fast in 30 minutes, and this temperature was kept 2 hours.
When reaction terminating, use HCl solution that the pH of mixture is adjusted to 3 to form catalyst granules.Also use the ion-exchange water washing of heat by the formed catalyst granules of isolated by filtration.
The ethanol oxidation catalysts that then gains comprised Pt/Ru alloy and tin oxide in baking oven 80 ℃ of following dryings with preparation.In ethanol oxidation catalyst, in the ethanol oxidation catalyst of 100 weight portions, the amount of the catalyst granules that is formed by Pt/Ru alloy and tin oxide is 80 weight portions.
Measurement is according to the XRD diffraction property of the ethanol oxidation catalyst of embodiment 1 preparation, and the result is shown in Figure 2.
With reference to Fig. 2, locate to observe the diffraction maximum of Pt at the Bragg angle (2 θ) of 30～50 degree, but do not observe the diffraction maximum of Ru.Therefore, can find out that Pt and Ru have formed alloy.Locate to observe the diffraction maximum of Sn at the Bragg angle (2 θ) of 34 degree.The composition of ethanol oxidation catalyst of the present invention can pass through inductively coupled plasma (ICP) and determine.
Embodiment 2: the preparation of ethanol oxidation catalyst
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio between Pt, the Sn and Ru is outside 2.8: 1.0: 0.2 in the catalyst of final preparation
Embodiment 3: the preparation of ethanol oxidation catalyst
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio between Pt, the Sn and Ru is outside 2.4: 1.0: 0.2 in the catalyst of final preparation.
Comparative Examples 1: the preparation of ethanol oxidation catalyst
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio between Pt, the Sn and Ru is outside 3.0: 1.0: 1.0 in the catalyst of final preparation.
Comparative Examples 2: the preparation of ethanol oxidation catalyst
With with embodiment 1 in identical method prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio between Pt, the Sn and Ru is outside 2.0: 1.0: 2.0 in the catalyst of final preparation.
Comparative Examples 3: the preparation of ethanol oxidation catalyst
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except the first time heating-up temperature be 120 ℃.
Comparative Examples 4: the preparation of ethanol oxidation catalyst
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except the second time heating-up temperature be 220 ℃.
Measured quantity is according to the average grain diameter and the distribution of particles of the ethanol oxidation catalyst that comprises Pt/Ru-oxidation Sn of embodiment 1-3 and Comparative Examples 1-4 preparation, and the result is shown in the table 1.
Table 1
| ??Pt∶SnO 2: Ru (mol ratio) | The average grain diameter of catalyst (nm) | Dispersed | |
| Embodiment 1 | ??2.6∶1.0∶0.4 | ??2.5 | Good |
| Embodiment 2 | ??2.8∶1.0∶0.2 | ??23 | Good |
| Embodiment 3 | ??2.4∶1.0∶0.6 | ??2.5 | Good |
| Comparative Examples 1 | ??3.0∶1.0∶1.0 | ??3.2 | Difference |
| Comparative Examples 2 | ??2.0∶1.0∶2.0 | ??3.2 | Difference |
| Comparative Examples 3 | ??3.0∶1.0∶1.0 | ??2.9 | Difference |
| Comparative Examples 4 | ??3.0∶1.0∶1.0 | ??3.1 | |
| Embodiment | |||
| 4 | ??2.1∶1.0∶0.4 | ??2.7 | Good |
| Embodiment 5 | ??2.9∶1.0∶0.6 | ??2.9 | Good |
| Comparative Examples 5 | ??2.0∶1.0∶0.4 | ??2.9 | Difference |
| Comparative Examples 6 | ??3.0∶1.0∶0.6 | ??3.1 | Difference |
The dispersiveness that shows in the table 1 is by using transmission electron microscopy (TTEM) to observe the cohesion average evaluation of catalyst granules.In this respect, when the amount of flocculated particle greater than based on the amount of whole catalyst granules 30% the time, it is poor that the cohesion of catalyst granules is defined as.
Embodiment 4: when Pt and Ru to SnO
2Mol ratio be 2.5: 1 o'clock
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio between Pt, the Sn and Ru is outside 2.1: 1.0: 0.4 in the catalyst of final preparation.
Embodiment 5: when Pt and Ru to SnO
2Mol ratio be 3.5: 1 o'clock
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The usefulness of O makes that the mol ratio between Pt, the Sn and Ru is outside 2.9: 1.0: 0.6 in the catalyst of final preparation.
Comparative Examples 5: when Pt and Ru to SnO
2Mol ratio less than 2.5: 1 o'clock
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio between Pt, the Sn and Ru is outside 2.0: 1.0: 0.4 in the catalyst of final preparation.
Comparative Examples 6: when Pt and Ru to SnO
2Mol ratio greater than 3.5: 1 o'clock
With with embodiment 1 in identical mode prepare ethanol oxidation catalyst, except regulating H
2PtCl
6XH
2O, SnCl
2And RuCl
3H
2The amount of O makes that the mol ratio between Pt, the Sn and Ru is outside 3.0: 1.0: 0.6 in the catalyst of final preparation.
With reference to table 1, to compare with the ethanol oxidation catalyst for preparing according to Comparative Examples 1-3, the ethanol oxidation catalyst for preparing according to embodiment 1-5 has smaller particle size and dispersed preferably.
Preparation example 1: the preparation of fuel cell
Use prepares the electrode of fuel cell according to the ethanol oxidation catalyst of embodiment 1 preparation.In loaded catalyst, in the loaded catalyst of 100 weight portions, the weight of Pt/Ru alloy is 80 weight portions.The amount of the ethanol oxidation catalyst of load is 3.8mg/cm on the anode electrode
2, the amount of the black catalyst of the Pt of load is 6.3mg/cm on the cathode electrode
2
Nafion 115 is as dielectric film, and the temperature of fuel cell is 50 ℃.In negative electrode, use air, and in anode, use the 1M ethanolic solution.
Preparation example 2 and 3
With with preparation example 1 in identical mode prepare fuel cell, replace the ethanol oxidation catalyst according to embodiment 1 preparation except using ethanol oxidation catalysts according to embodiment 2 and 3 preparations.
Comparative preparation example 2 and 3
With with preparation example 1 in identical mode prepare fuel cell, prepare the anode except using according to ethanol oxidation catalyst according to Comparative Examples 1-4 preparation.
Measurement is according to the peak power of the fuel cell of preparation example 1-3 and comparative preparation example 1-4 preparation, and the result is shown in the following table 2.
Table 2
| Power density (mW/cm under 40 ℃ 2) | |
| Preparation example 1 | ??23 |
| Preparation example 2 | ??18 |
| Preparation example 3 | ??20 |
| Comparative preparation example 1 | ??10 |
| Comparative preparation example 2 | ??8 |
| Comparative preparation example 3 | ??6 |
| Comparative preparation example 4 | ??≈0 |
With reference to table 2, the fuel cell for preparing according to preparation example 1-3 has the fuel cell good power characteristic of beguine according to comparative preparation example 1-4 preparation.
Measurement is according to the fuel cell of preparation example 1 and comparative preparation example 1 preparation cell voltage and the power density with respect to current density, and the result is shown in Figure 3.
With reference to Fig. 3, has and compares the power density of remarkable big (about twice is big) according to the fuel cell of preparation example 1 preparation according to the fuel cell of comparative preparation example 1 preparation.Therefore, as can be seen the activity of ethanol oxidation catalyst prepared in accordance with the present invention greater than the activity of conventional catalyst.
Though shown particularly and described the present invention with reference to illustrative embodiments of the present invention, but it will be understood by those skilled in the art that and wherein can carry out the various variations on form and the details and do not break away from the spirit and scope of the present invention that limit by claims.
Claims (13)
1. the ethanol oxidation catalyst that comprises Pt/Ru alloy and tin oxide, wherein the mol ratio of Pt/Ru alloy and tin oxide is 2.5-3.5: 1.
2. the ethanol oxidation catalyst of claim 1, wherein the mol ratio of Pt and Ru is 3-15 in described Pt/Ru alloy: 1.
3. the ethanol oxidation catalyst of claim 1 wherein has when shining
During the Cu K α X-ray of wavelength, locate to observe main peak at the Bragg angles (2 θ) of 30 degree-50 degree.
4. the ethanol oxidation catalyst of claim 1 further comprises carrier, and described Pt/Ru alloy and described tin oxide load on this carrier.
5. the ethanol oxidation catalyst of claim 4, wherein in the ethanol oxidation catalyst of 100 weight portions, the amount of described carrier is about 90 weight portions of about 50-.
6. method of making ethanol oxidation catalyst, described method comprises:
By preparing Pt precursor and Ru precursor and Sn precursor and respectively described precursor is dissolved in first solvent separately, and mix the solution of described precursor and prepare metal salt solution;
By catalyst carrier and solvent are prepared carrier solution;
By this metal salt solution and this carrier solution are mixed, and the pH that regulates mixture prepares loaded catalyst with the particle of supported catalyst on this catalyst carrier;
Carry out the heat treatment process first time by heat treatment gains under the about 70 ℃ temperature of about 50-;
Carry out the heat treatment process second time by heat treatment gains under the about 160 ℃ temperature of about 125-;
Regulate the pH of gains; With
Separation is also washed this loaded catalyst.
7. the method for claim 6, wherein said first time, the rate of heat addition of heat treatment process was about 3-7 ℃/min.
8. the method for claim 6, wherein said second time, the rate of heat addition of heat treatment process was about 3-7 ℃/min.
9. the method for claim 6, the mol ratio of the Ru in Pt in the wherein said Pt precursor and the described Ru precursor is about 3: about 15: 1 of 1-.
10. the method for claim 6 wherein, during with the particle of supported catalyst on this catalyst carrier, is adjusted to 10-14 with pH at the pH that regulates mixture.
11. the method for claim 6 wherein, in the pH that regulates gains, is adjusted to 1-5 with pH.
12. an electrode that is used for fuel cell, it comprises according to each ethanol oxidation catalyst among the claim 1-5.
13. a fuel cell, it comprises: negative electrode; Anode; And the dielectric film between this negative electrode and this anode,
Wherein at least one of this negative electrode and this anode comprises according to each ethanol oxidation catalyst among the claim 1-5.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810173761A CN101683614A (en) | 2008-09-26 | 2008-09-26 | Ethanol oxidation catalyst, manufacturing method thereof and fuel cell using same |
| KR1020080119937A KR101015505B1 (en) | 2008-09-26 | 2008-11-28 | Alcohol oxidation catalyst, manufacturing method thereof, and fuel cell using the same |
| US12/567,038 US20100081036A1 (en) | 2008-09-26 | 2009-09-25 | Alcohol oxidation catalyst, method of manufacturing the same, and fuel cell using the alcohol oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200810173761A CN101683614A (en) | 2008-09-26 | 2008-09-26 | Ethanol oxidation catalyst, manufacturing method thereof and fuel cell using same |
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| CN200810173761A Pending CN101683614A (en) | 2008-09-26 | 2008-09-26 | Ethanol oxidation catalyst, manufacturing method thereof and fuel cell using same |
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|---|---|---|---|---|
| CN112825357A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Pt-based multi-component transition metal alloy nano electro-catalyst, preparation and application |
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| JP2004363056A (en) | 2003-06-06 | 2004-12-24 | Nissan Motor Co Ltd | Catalyst carrying electrode for polymer electrolyte fuel cell and its manufacturing method |
| US7897293B2 (en) | 2003-10-20 | 2011-03-01 | The United States Of America As Represented By The Secretary Of The Navy | Platinum-impregnated hydrous tin oxide catalysts |
| KR100552697B1 (en) | 2003-11-13 | 2006-02-20 | 삼성에스디아이 주식회사 | Metal oxide-carbon composite catalyst support and fuel cell comprising the same |
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| CN112825357A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Pt-based multi-component transition metal alloy nano electro-catalyst, preparation and application |
| CN112825357B (en) * | 2019-11-21 | 2022-05-06 | 中国科学院大连化学物理研究所 | Pt-based multi-component transition metal alloy nano electro-catalyst, preparation and application |
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| KR20100035564A (en) | 2010-04-05 |
| KR101015505B1 (en) | 2011-02-16 |
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