CN101224435A - Supported PtRu alloy catalyst and preparing method thereof - Google Patents
Supported PtRu alloy catalyst and preparing method thereof Download PDFInfo
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- CN101224435A CN101224435A CNA2007100012808A CN200710001280A CN101224435A CN 101224435 A CN101224435 A CN 101224435A CN A2007100012808 A CNA2007100012808 A CN A2007100012808A CN 200710001280 A CN200710001280 A CN 200710001280A CN 101224435 A CN101224435 A CN 101224435A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 229910002849 PtRu Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 title claims description 44
- 239000000956 alloy Substances 0.000 title claims description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
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- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
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- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
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- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B01J35/40—
-
- 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
-
- 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]
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The preparation of a supported PtRu alloying catalyst is realized by the following steps: First, the precursor solutions of Pt and Ru are mixed to prepare a metal salt solution, then the pH value of the solution is adjusted, and the solution is heated, so as to obtain a catalyst colloidal solution. Carriers are dispersed to a solution and mixed with the catalyst colloidal solution, and then the pH value of the mixed solution is adjusted for facilitating the deposition of the catalyst colloidal particles on the carriers. The catalyst is filtered, washed and heat treated in a reducing atmosphere with appropriate proportions to obtain the supported PtRu alloying catalyst. The invention improves the crystallinity of PtRu catalyst by combing the polyol method and heat treating in a reducing atmosphere, removes adsorption species on the catalyst surface effectively during polyol method process and also improves the methanol oxidability and the resistance of CO poisoning of alloying catalyst.
Description
Technical field
The present invention relates to fuel cell technology, particularly a kind of supported PtRu alloy catalyst and preparation method thereof.
Background technology
DMFC (DMFC) is a kind of electrochemical reaction appts that the chemical energy of fuel (methyl alcohol) is converted into electric energy, have theoretical energy density height, simple in structure and advantages of environment protection, have broad application prospects at aspects such as electronic equipment and compact powers.
Yet, the business-like major technique challenge of obstruction DMFC at present is that the catalytic oxidation speed of (＜100 ℃) methyl alcohol under the low temperature is slower, and noble metal catalyst is easily poisoned by CO class intermediate product, cause battery performance and service life still undesirable, therefore research and develop the high activity methanol oxidation catalyst and improve its anti-CO poisoning capability the research focus that always is DMFC it
PtRu is the DMFC anode catalyst system the most widely of research at present.The anti-CO mechanism of poisoning of PtRu catalyst is followed difunctional mechanism: be adsorbed on above the Pt-CO species and be adsorbed on above the Ru-the OH species react, and generate H
2O and CO
2(seeing accompanying drawing 1).This just requires Pt atom and Ru atom contiguous as far as possible, and therefore, the PtRu catalyst of alloy attitude is optimal.The experimental results shows, when the mol ratio of Pt and Ru is 1: 1 or during near 1: 1, catalyst has the highest CO resistance performance.And the lattice paprmeter of PtRu alloy should be between 3.856-3.885 in the prepared catalyst.If not in this scope, difunctional mechanism will be difficult to satisfy.The metallic particles diameter of catalyst should be between 1.5-5nm.If particle diameter is greater than 5nm, specific surface area of catalyst reduces, the active reduction.If the catalyst granules diameter is less than 1.5nm, catalyst particle can be assembled easily.
Document 1[USP 6339038] the middle method that proposes a kind of PtRu/C of preparation catalyst: at first prepare the Pt/C catalyst, add more weak reducing agent (Ru can not be reduced) and the precursor solution of Ru then, under the catalytic action of Pt/C catalyst, earlier with the reducing agent oxidation, discharge electronics, under the effect of ejected electron Ru is being reduced. because the electronics that discharges all is near the Pt active sites, thereby obtain the contiguous catalyst of PtRu active sites, according to difunctional mechanism, will help the oxidation of CO.But the PtRu that this method obtains does not form alloy, thereby Ru runs off easily, and complicated operation, and control is had relatively high expectations to condition.
Document 2[USP 6551960] introduced a kind of supported PtRu Preparation of catalysts method: two kinds of metal precursors are dissolved in respectively in the polyalcohol, add carbon carrier, reducing metal and depositing on the carbon carrier under the reflux state.The catalyst loadings of preparation is low, can not be higher than 50wt.%, and the alloy degree is lower.
Document 3[WO2006008001] introduced a kind of PtRu alloy catalyst preparation method, can prepare the PtRu catalyst of different loads amount, and the alloy degree is higher.But institute's narration process is wayward, and metal granularity skewness.
Document 4[USP6007934] in adopt flood-reduce method, utilize formaldehyde with the metal precursor aqueous solution reduction of Pt and Ru and deposit on the carbon carrier, prepare the supported PtRu catalyst.Infusion process can not prepare the catalyst of high content of metal, prepared content of metal is lower than 40wt.%, and metallic particles is skewness on carrier, and do not form alloy between the metal, the applicant thinks that non-alloy helps the CO oxidation, but Ru runs off easily in unalloyed PtRu catalyst, and is bigger to the stability and the life-span influence of catalyst.
Document 5[Journal of New Materials for Electrochemical Systems, 3,199-206 (2000)] people such as Bonnemann introduced a kind of preparation method of PtRu colloid, and prepared PtRu/C catalyst alloy degree is higher, and granularity is less.But adopt the bigger nonaqueous solvents of toxicity in the experiment, have greater environmental impacts.And prepared catalyst granules surface coats one deck blocking group, and activity of such catalysts is had considerable influence.
Summary of the invention
The object of the present invention is to provide a kind of supported PtRu alloy catalyst and preparation method thereof.This catalyst biggest advantage is to have higher anti-CO poisoning capability and methanol oxidation activity, has improved fuel battery performance.
For achieving the above object, technical solution of the present invention provides a kind of supported PtRu alloy catalyst and preparation method thereof.
The preparation method of described supported PtRu alloy catalyst is characterized in that, comprises the following steps:
The first step is dissolved in the presoma of Pt and Ru respectively in first kind of solvent, mixes to form metal salt solution.First kind of solvent can be the mixed solution of water or water and polyalcohol.Wherein water can be deionized water, and polyalcohol can be ethylene glycol or glycerine.According to one embodiment of present invention, the presoma of Pt and Ru can be dissolved in the polyalcohol.When the presoma of dissolving Pt, the mass ratio of solvent and Pt is between 300-900; When the presoma of dissolving Ru, the mass ratio of solvent and Pt is between 700-260.The presoma of Pt and Ru can be any salt soluble in water, such as chloride, sulfate or the nitrate of Pt and Ru.
Second step, the pH value of regulating above-mentioned metal salt solution., can use aqueous slkali to regulate the pH value here, such as NaOH, NH
4OH, KOH or Ca (OH)
2With the metal salt solution heat temperature raising after the adjusting of pH value, metal ion is reduced, and forms catalyst colloidal solution, and reduction temperature is between 110-190 ℃.
The 3rd step was dispersed in catalyst carrier in second kind of solvent, formed carrier solution.Carrier can be material with carbon element or molecular sieve, and perhaps silica etc. is good with material with carbon element or molecular sieve wherein.Material with carbon element can be graphite, carbon dust, acetylene black, carbon black, active carbon, mesoporous carbon, CNT (carbon nanotubes), carbon nano-fiber (carbon nanofibers), carbon nanohorn (carbon nanohorns), carbon nano ring (carbon nanorings), carbon nanocoils (carbonnanowires) and fullerene (C60).Second kind of solvent can be ethylene glycol, deionized water, glycerine etc.
The 4th step, catalyst colloidal solution is mixed with carrier solution, regulate the pH value of mixed solution, the catalyst colloidal solid is deposited on the carrier.
In the 5th step, filtration, washing and dry catalyst are heat-treated in a certain proportion of reducing atmosphere then.
The preparation method of described supported PtRu alloy catalyst is characterized in that, when catalyst is heat-treated in a certain proportion of reducing atmosphere the volume ratio of hydrogen between 5-50%, further, between 8%-10%.If hydrogen volume content is lower than 5%, reduction is not obvious; If hydrogen volume content is higher than 50%, reduction rate is too fast, can cause the gathering of catalyst granules.
The preparation method of described supported PtRu alloy catalyst is characterized in that, a certain proportion of reducing atmosphere comprised a kind of in hydrogen and argon gas, nitrogen and the helium when catalyst was heat-treated.
The preparation method of described supported PtRu alloy catalyst is characterized in that, heat treatment temperature is between 100-500 ℃.If treatment temperature is lower than 100 ℃, have only the Ru of small part and Pt to form alloy, catalyst shows lower CO resistance performance; If treatment temperature is higher than 500 ℃, catalyst granules increases, and has reduced the utilization rate of catalyst.
The preparation method of described supported PtRu alloy catalyst is characterized in that, heat treatment time is between 20-180 minute.
The preparation method of described supported PtRu alloy catalyst is characterized in that, in the prepared metal salt solution, Pt in Pt and the Ru precursor: the Ru atomic ratio is 8: 2-3: between 7.If the mol ratio of Pt and Ru is not in this scope, just not in this scope, this may cause the decline of its anti-CO poisoning capability to the mol ratio of Pt and Ru in the PtRu alloy catalyst.
The preparation method of described supported PtRu alloy catalyst is characterized in that, metal salt solution pH value is adjusted between the 10-14.If the pH value is lower than 10, may causes metallic reducing incomplete, thereby reduce the noble metal load capacity; If the pH value is higher than 14, may cause growing up of catalyst granules.
The preparation method of described supported PtRu alloy catalyst is characterized in that, mixed solution pH value is adjusted between the 1-5.If the pH value of solution value is lower than 1,, may cause the loss of noble metal because acidity is excessive; If the pH value of solution value is higher than 5, catalyst granules and carrier interphase interaction may reduce, and cause catalyst granules load fully.
The preparation method of described supported PtRu alloy catalyst is characterized in that, the lattice parameter of prepared supported PtRu alloy catalyst is at 3.856-3.855
Between, particle size is between 2-5nm.
The preparation method of described supported PtRu alloy catalyst is characterized in that, the mass percent of Pt and Ru is between 50-90% in the prepared supported PtRu alloy catalyst.If mass percent is lower than 50%, Catalytic Layer thickness is bigger when the preparation fuel cell electrode, causes resistance excessive; If be higher than 90%, catalyst particle size is greater than 5nm, and is easy to generate gathering, causes specific surface area of catalyst to reduce, the active reduction.
The present invention also provides a kind of fuel cell electrode, comprises the prepared supported PtRu alloy catalyst of said method in this electrode.
The present invention also provides a kind of fuel cell, the anode that comprise negative electrode, constitutes by the prepared supported PtRu alloy catalyst of said method and place negative electrode and anode between dielectric film.
Advantage of the present invention and effect:
(1) two constituent elements are evenly distributed in Zhi Bei the supported PtRu alloy catalyst, and the catalyst granules particle diameter is little and be evenly distributed on carrier.
(2) combine handling in polyalcohol method and the reducing atmosphere, improved the degree of crystallinity of PtRu catalyst, and effectively removed the adsorbing species of catalyst surface in polyalcohol method process, improved the methanol oxidation ability of alloy catalyst and the ability that anti-CO poisons.
Description of drawings:
Accompanying drawing 1 is the principle schematic that the anti-CO of PtRu alloy catalyst poisons.
Accompanying drawing 2 is the flow chart according to preparation PtRu alloy catalyst among this patent embodiment.
Accompanying drawing 3 be the PtRu alloy catalyst for preparing according to embodiment 1,2 and comparative example 2,3 XRD spectra relatively.
Accompanying drawing 4 is EDX spectrogram and analysis results of the PtRu alloy catalyst for preparing according to embodiment 1.
The specific embodiment
In order to further specify the present invention, enumerate following examples, do not limit scope of invention.
Among below the embodiment and comparative example, the granular size of catalyst is calculated by XRD result.The computing formula of using is the Scherrer formula:
The X ray wavelength that is to use of λ wherein, k is the Scherrer constant, θ is a Bragg angle.B
dIt is the peak width of doing of diffraction maximum.Lattice paprmeter is then calculated by the Bragg formula:
The X ray wavelength that is to use of λ wherein, θ
MaxFor calculating the position of the diffraction maximum that is adopted.
The specific embodiment
Embodiment 1
With 1g hydration chloroplatinic acid (H
2PtCl6xH
2O) (metal Pt quality percentage composition 37%) and 0.5g hydrate ruthenium trichloride (metal Ru quality percentage composition 37%) join in the 25ml ethylene glycol, stir to form hybrid metal solution.The 0.370g carbon black is joined in the 100g ethylene glycol, and stirring makes and is uniformly dispersed, and forms carrier solution.Dropwise add NaOH solution in hybrid metal solution, reconciling the pH value of solution value is 13.Above-mentioned solution is put into oil bath, be warming up to 180 ℃ and kept 30 minutes, reduce to 170 ℃ then and kept 3 hours, metal is reduced, and forms black catalyst colloidal solution.In catalyst colloidal solution, add carrier solution, mix, and be 3 with hydrochloric acid conditioning solution pH, then after filtration, deionized water washing, 80 ℃ of dryings of vacuum.The catalyst that obtains is 10% hydrogen-argon-mixed 200 ℃ through the hydrogen volume mark in tube furnace handled 2 hours down, obtained the PtRu alloy catalyst.
Embodiment 2
With 1g hydration chloroplatinic acid (H
2PtCl6xH
2O) (metal Pt quality percentage composition 37%) and 0.5g hydrate ruthenium trichloride (metal Ru quality percentage composition 37%) join in the 25ml ethylene glycol, stir to form hybrid metal solution.The 0.140g carbon black is joined in the 100g ethylene glycol, and stirring makes and is uniformly dispersed, and forms carrier solution.Dropwise add NaOH solution in hybrid metal solution, reconciling the pH value of solution value is 13.Above-mentioned solution is put into oil bath, be warming up to 180 ℃ and kept 30 minutes, reduce to 170 ℃ then and kept 3 hours, metal is reduced, and forms black catalyst colloidal solution.In catalyst colloidal solution, add carrier solution, mix, and be 3 with hydrochloric acid conditioning solution pH, then after filtration, deionized water washing, 80 ℃ of dryings of vacuum.The catalyst that obtains is 10% hydrogen-argon-mixed 200 ℃ through the hydrogen volume mark in tube furnace handled 2 hours down, obtained the PtRu alloy catalyst.
Embodiment 3
Catalyst preparation process is with embodiment 1.Heat-treat condition is to be 10% hydrogen-argon-mixed 200 ℃ at the hydrogen volume mark to handle 30 minutes down.
Embodiment 4
Catalyst preparation process is with embodiment 1.Heat-treat condition is to be 8% hydrogen-argon-mixed 200 ℃ at the hydrogen volume mark to handle 2 hours down.
Embodiment 5
Catalyst preparation process is with embodiment 1.Heat-treat condition is to be 40% hydrogen-argon-mixed 200 ℃ at the hydrogen volume mark to handle 2 hours down.
Embodiment 6
Catalyst preparation process is with embodiment 1.Heat-treat condition is to be 50% hydrogen-argon-mixed 200 ℃ at the hydrogen volume mark to handle 2 hours down.
Comparative example 1
Catalyst preparation process is with embodiment 1.Heat-treat condition is to handle 30 minutes under 200 ℃ in pure hydrogen atmosphere.
Comparative example 2
Catalyst preparation process is with embodiment 1.Prepared catalyst is not heat-treated.
Comparative example 3
Catalyst preparation process is with embodiment 1.Heat-treat condition be the hydrogen volume mark be 10% hydrogen-argon-mixed in 600 ℃ handled 2 hours down.
Fig. 3 has provided the XRD spectra according to the prepared PtRu/C catalyst of embodiment 1,2 and comparative example 2,3.Its result of calculation is listed in the table 1.Wherein average grain diameter is calculated by Scherrer, and lattice paprmeter is then calculated by the Bragg formula.As can be seen, with the increase of catalyst loadings, the catalyst granules particle diameter increases, but its size still can be controlled in about 3nm.And heat treatment makes catalyst particle size increase to some extent.When heat treatment temperature surpassed 500 ℃, the catalyst particle size increase was bigger, surpassed 5nm.Fig. 4 is the EDX spectrogram according to the prepared PtRu/C catalyst of embodiment 1. by the EDX spectrum analysis, Pt in the prepared PtRu/C alloy catalyst: the Ru atomic ratio is 53: 46, and is very approaching with rate of charge 1: 1.
The XRD result of calculation of table 1 different catalysts
The methanol oxidation activity that adopts electrochemical method to test embodiment 1-5 and the prepared PtRu/C catalyst of comparative example 1-2, concrete result of calculation is listed in the table 2.
The methanol oxidation specific mass specific activity of table 2 different catalysts
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment | Embodiment 6 | Comparative example 1 | Comparative example | Comparative example 3 | |
| Hydrogen volume content (vol.%) | 10 | 10 | 10 | 8 | 40 | 50 | 100 | 10 | 10 |
| Heat treatment temperature (℃) | 200 | 200 | 200 | 200 | 200 | 200 | 200 | Without heat treatment | 600 |
| Specific mass activity (A/g PtRu) | 59 | 55 | 54 | 48 | 42 | 37 | 35 | 35 | 29 |
Claims (10)
1. the preparation method of a supported PtRu alloy catalyst is characterized in that: at first mix Pt and the Ru precursor solution prepares metal salt solution, regulate the pH value of metal salt solution, heat, make catalyst colloidal solution; Then carrier is distributed in the solvent, mixes, regulate the pH value of mixed solution, the catalyst colloidal solid is deposited on the carrier with catalyst colloidal solution; Filter, washing catalyst, and in reducing atmosphere, heat-treat, obtain supported PtRu alloy catalyst, and in the described supported PtRu alloy catalyst mass percent of Pt and Ru between 50-90%; The volume ratio of hydrogen is 5-50% in the described heat treated reducing atmosphere.
2. according to the described preparation method of claim 1, the reducing atmosphere during described heat treatment comprises a kind of in hydrogen and argon gas, nitrogen and the helium.
3. according to the described preparation method of claim 1, described heat treatment temperature is 100-500 ℃.
4. according to the described preparation method of claim 1, described heat treatment time is 20-180 minute.
5. according to the described preparation method of claim 1, in the described metal salt solution, Pt in Pt and the Ru precursor: the Ru atomic ratio is 8: 2-3: 7.
6. according to the described preparation method of claim 1, described metal salt solution pH value is adjusted between the 10-14.
7. according to the described preparation method of claim 1, described mixed solution pH value is adjusted between the 1-5.
8. according to the described preparation method of claim 9, the lattice parameter of described supported PtRu alloy catalyst is 3.856-3.885
Particle size is 2-5nm.
9. a fuel cell electrode comprises the prepared supported PtRu alloy catalyst of the described method of claim 1 in this electrode.
10. fuel cell, comprise negative electrode, by have the anode that the prepared supported PtRu alloy catalyst of the described method of claim 1 constitutes and place negative electrode and anode between dielectric film.
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| CN114447352A (en) * | 2022-01-25 | 2022-05-06 | 江苏擎动新能源科技有限公司 | PtRu/C catalyst and preparation method thereof |
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| KR100868756B1 (en) | 2008-11-17 |
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