CN106898785A - A kind of preparation method of surfactant-modified fuel battery anode catalyst - Google Patents
A kind of preparation method of surfactant-modified fuel battery anode catalyst Download PDFInfo
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- CN106898785A CN106898785A CN201710131845.8A CN201710131845A CN106898785A CN 106898785 A CN106898785 A CN 106898785A CN 201710131845 A CN201710131845 A CN 201710131845A CN 106898785 A CN106898785 A CN 106898785A
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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
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
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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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- 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
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Abstract
The invention discloses a kind of preparation method of surfactant-modified fuel battery anode catalyst, belong to fuel cell catalyst technical field of material.Preparing raw material is constituted：Surfactant, Ca (NO3)2·4H2O, TEOS, activated carbon, the acid of chlorine palladium and reducing agent.Wherein surfactant is one or more in CTAB, CTAC, P123 and F127, and Ca elements are 1 with the mol ratio of Si elements:3~3:1, Ca element is 0.5 with the mol ratio of surfactant:1~1:1.Surfactant-modified CaSiO is obtained by thermal decomposition method3C complex carriers, by liquid phase reduction on complex carrier supported palladium nanocatalyst.The palladium nanocatalyst obtained in the present invention is uniformly dispersed on carrier, and particle size is homogeneous, has catalysis activity higher to alcohols.Preparing raw material of the present invention is simple and easy to get, process stabilizing, reaches industrialized condition.
Description
Technical field
The invention belongs to fuel cell catalyst technical field of material, and in particular to a kind of surfactant-modified combustion
Expect the preparation method of cell anode catalyst.
Background technology
Fuel cell is considered as 21 century first-selected clean, efficient generation technology, will be changed by electrochemical reaction
Can be converted into the device of electric energy, can directly use the liquid fuels such as methyl alcohol, ethanol as the unstripped gas of fuel cell,
Environment is not almost polluted.Catalyst is one of critical material in fuel cell, the cost of catalyst account for fuel cell into
This 1/3, the commercialization of following clean energy resource this for fuel cell has very important significance.On fuel cell sun
The research of electrode catalyst is concentrated mainly on Pt systems connection metal, and Pt is the fuel-cell catalyst for being used earliest.However, due to
Fuel cell electrochemical oxidation process is complicated, and especially CO can be in Pt adsorptions cause catalyst to many intermediate products
Poison, significantly reduces the catalysis activity and stability of Pt, while contents of the Pt in the earth is seldom, it is expensive, in recent years, grind
Study carefully personnel and attempt the palladium-based catalyst that various methods prepare various active component high degree of dispersion.Property of the catalyst carrier to catalyst
Can also important, carrier first can be conducive to the dispersion of nano particle, so as to improve its utilization rate and current density；
During carrier can also participate in catalytic reaction simultaneously, such as the intermediate product for being reacted with some is had an effect, so as to influence to urge
The catalytic performance of agent.As the carrier of fuel-cell catalyst, generally there is excellent electric conductivity, be beneficial to reaction
Electron transmission；Larger specific surface area, can make nano material dispersed；Good decay resistance, can be in strong acid, strong
Worked for a long time in the media such as alkali, and be resistant to uniform temperature and electric current；Preferable binding ability, can make catalyst granules stabilization exist
On carrier.
The content of the invention
In order to solve the above problems, the invention provides a kind of surfactant-modified fuel battery anode catalyst
Preparation method.By adding suitable surfactant, carrier material is modified, palladium nanocatalyst can be significantly improved
Particle and then improves its catalytic performance in the dispersiveness of carrier surface.
The present invention is implemented by following technical solution：
A kind of preparation method of surfactant-modified fuel battery anode catalyst, specifically includes following steps：
（1）By surfactant and Ca (NO3)2·4H2Ultrasound makes to be placed in baking oven after its is dispersed during O, TEOS are dissolved in solvent
Dry mixture A；
（2）By step（1）Gained mixture A is positioned over 500-600 DEG C of program control stove and is incubated 2 hours, obtains mixture B；
（3）By step（2）Gained mixture B is added in chlorine palladium acid solution with absorbent charcoal material, quickly stirs 4h, fully dispersed to obtain
Solution A；
（4）Dissolve reduce agent in water to obtain solution B；
（5）By step（4）Resulting solution B is slowly added dropwise step（3）In the solution A of gained, at room temperature after magnetic agitation 4h
Centrifuge washing is dried, and obtains final product calcium silicates with activated carbon supported palladium nano-catalyst material.
The surfactant is one or more in CTAB, CTAC, P123 and F127.
Step（1）Described in solvent be absolute ethyl alcohol.
Step（1）In, Ca (NO3)2·4H2The mol ratio of O and TEOS is 1:3~3:1.
Step（1）In, Ca (NO3)2·4H2O is 0.5 with the mol ratio of surfactant:1~1:1.
The concentration of the chlorine palladium acid solution is 18.9 mmol/L；The concentration of the solution B is 0.1 mol/L.
Step（3）The mass ratio of middle mixture B, absorbent charcoal material and chlorine palladium acid solution is 1:1:1.
Solution A is 1 with the volume ratio of solution B:2.
Step（4）Described in reducing agent be NaBH4。
Sample centrifuge washing solvent for use is absolute ethyl alcohol or water in the step.
Remarkable advantage of the invention is：The CaSiO of different-shape is obtained by surfactant3- C complex carriers, show
The dispersiveness for improving palladium nano-catalyst particles on carrier is write, the palladium nanometer of size uniform is obtained in combination with liquid phase reduction
Particle, has catalysis activity higher to Aalcohols fuels such as ethanol and methyl alcohol；In addition, the CaSiO in complex carrier3Can be notable
Absorption of the catalyst to hydroxyl is improved, accelerates intermediate product CO in the desorption process of catalyst surface, so as to be effectively improved catalysis
The stability of agent.Raw material of the present invention is simple and easy to get, stable preparation process, has reached practical and industrialized condition.
Brief description of the drawings
Fig. 1 is the SEM figures of fuel battery anode catalyst material.
Specific embodiment
The present invention is further described below by embodiment.
Embodiment 1：The preparation of material
（1）According to Ca (NO3)2·4H2O and Surfactant CTAB mol ratio 0.5:1, with TEOS mol ratios 1:3 to weigh raw material molten
Ultrasound makes to be placed in after its is dispersed in baking oven and dries in absolute ethyl alcohol, obtains mixture A；
（2）By step（1）Gained mixture A is positioned in program control stove 500 DEG C and is incubated 2 hours, obtains mixture B；
（3）By step（2）Gained mixture B is added in 18.9 mmol/L chlorine palladium acid solutions with absorbent charcoal material, wherein mixture
The mass ratio of B, absorbent charcoal material and chlorine palladium acid solution is 1:1:1,4h is then quickly stirred at room temperature, it is fully dispersed to obtain solution A；
（4）By reducing agent NaBH4Soluble in water to obtain solution B, the concentration of solution B is 0.1 mol/L；
（5）Solution B is slowly added dropwise in solution A, solution A is 1 with the volume ratio of solution B:2, magnetic agitation 4h at room temperature
Wash centrifugal drying with water afterwards and obtain final product calcium silicates with activated carbon supported palladium nano-catalyst material.
Fig. 1 schemes for the SEM of fuel battery anode catalyst material.As seen from the figure, palladium nanocatalyst is uniform on carrier
Dispersion.Gained catalyst is 14 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）Decline
Lapse rate is only 18%.
Embodiment 2：The preparation of material
（1）According to Ca (NO3)2·4H2O and surfactant CTAC mol ratios 1:1, with TEOS mol ratios 1:3 weigh raw material is dissolved in
Ultrasound makes to be placed in after its is dispersed in baking oven and dries in absolute ethyl alcohol, obtain mixture A；
（2）By step（1）Gained mixture A is positioned in program control stove 550 DEG C and is incubated 2 hours, obtains mixture B；
（3）By step（2）Gained mixture B is added in 18.9 mmol/L chlorine palladium acid solutions with absorbent charcoal material, wherein mixture
The mass ratio of B, absorbent charcoal material and chlorine palladium acid solution is 1:1:1,4h is then quickly stirred at room temperature, it is fully dispersed to obtain solution A；
（4）By reducing agent NaBH4Soluble in water to obtain solution B, the concentration of solution B is 0.1 mol/L；
（5）Solution B is slowly added dropwise in solution A, solution A is 1 with the volume ratio of solution B:2, magnetic agitation 4h at room temperature
Calcium silicates is drying to obtain with activated carbon supported palladium nano-catalyst material with absolute ethyl alcohol centrifuge washing afterwards.Gained catalyst pair
The specific activity of alcohol catalysis is 12 mAcm-2, continuous operation 12 hours（65 DEG C, 0.65V）Attenuation rate be only 15%.
Embodiment 3：The preparation of material
（1）According to Ca (NO3)2·4H2O and surfactant P123 mol ratios 0.5:1, with TEOS mol ratios 3:1 to weigh raw material molten
Ultrasound makes to be placed in after its is dispersed in baking oven and dries in absolute ethyl alcohol, obtain mixture A；
（2）By step（1）Gained mixture A is positioned in program control stove 600 DEG C and is incubated 2 hours, obtains mixture B；
（3）By step（2）Gained mixture B is added in 18.9 mmol/L chlorine palladium acid solutions with absorbent charcoal material, wherein mixture
The mass ratio of B, absorbent charcoal material and chlorine palladium acid solution is 1:1:1,4h is then quickly stirred at room temperature, it is fully dispersed to obtain solution
A；
（4）By reducing agent NaBH4Soluble in water to obtain solution B, the concentration of solution B is 0.1 mol/L；
（5）Solution B is slowly added dropwise in solution A, solution A is 1 with the volume ratio of solution B:2, magnetic agitation 4h at room temperature
Wash centrifugal drying with water afterwards and obtain final product calcium silicates with activated carbon supported palladium nano-catalyst material.Gained catalyst is to alcohol catalysis
Specific activity be 15 mAcm-2, continuous operation 12 hours（65 DEG C, 0.65V）Attenuation rate be only 22%.
Embodiment 4：The preparation of material
（1）According to Ca (NO3)2·4H2O and surfactant F127 mol ratios 1:1, with TEOS mol ratios 1:1 weighs raw material is dissolved in
Ultrasound makes to be placed in after its is dispersed in baking oven and dries in absolute ethyl alcohol, obtains mixture A；
（2）By step（1）Gained mixture A is positioned in program control stove 600 DEG C and is incubated 2 hours, obtains mixture B；
（3）By step（2）Gained mixture B is added in 18.9 mmol/L chlorine palladium acid solutions with absorbent charcoal material, wherein mixture
The mass ratio of B, absorbent charcoal material and chlorine palladium acid solution is 1:1:1,4h is then quickly stirred at room temperature, it is fully dispersed to obtain solution A；
（4）By reducing agent NaBH4Soluble in water to obtain solution B, the concentration of solution B is 0.1 mol/L；
（5）Solution B is slowly added dropwise in solution A, solution A is 1 with the volume ratio of solution B:2, magnetic agitation 4h at room temperature
Calcium silicates is drying to obtain with activated carbon supported palladium nano-catalyst material with absolute ethyl alcohol centrifuge washing afterwards.Gained catalyst pair
The specific activity of alcohol catalysis is 13 mAcm-2, continuous operation 12 hours（65 DEG C, 0.65V）Attenuation rate be only 16%.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (9)
1. a kind of preparation method of surfactant-modified fuel battery anode catalyst, it is characterised in that：Specifically include with
Lower step：
（1）By surfactant and Ca (NO3)2·4H2Ultrasound makes to be placed in baking oven after its is dispersed during O, TEOS are dissolved in solvent
Dry mixture A；
（2）By step（1）Gained mixture A is positioned over 500-600 DEG C of program control stove and is incubated 2 hours, obtains mixture B；
（3）By step（2）Gained mixture B is added in chlorine palladium acid solution with absorbent charcoal material, quickly stirs 4h, fully dispersed to obtain
Solution A；
（4）Dissolve reduce agent in water to obtain solution B；
（5）By step（4）Resulting solution B is slowly added dropwise step（3）In the solution A of gained, at room temperature after magnetic agitation 4h
Centrifuge washing is dried, and obtains final product calcium silicates with activated carbon supported palladium nano-catalyst material.
2. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：The surfactant is one or more in CTAB, CTAC, P123 and F127.
3. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：Step（1）Described in solvent be absolute ethyl alcohol.
4. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：Step（1）In, Ca (NO3)2·4H2The mol ratio of O and TEOS is 1:3~3:1.
5. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：Step（1）In, Ca (NO3)2·4H2O is 0.5 with the mol ratio of surfactant:1~1:1.
6. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：The concentration of the chlorine palladium acid solution is 18.9 mmol/L；The concentration of the solution B is 0.1 mol/L.
7. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：Step（3）The mass ratio of middle mixture B, absorbent charcoal material and chlorine palladium acid solution is 1:1:1.
8. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：Solution A is 1 with the volume ratio of solution B:2.
9. the preparation method of a kind of surfactant-modified fuel battery anode catalyst according to claim 1, its
It is characterised by：Step（4）Described in reducing agent be NaBH4。
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| CN201710131845.8A CN106898785A (en) | 2017-03-07 | 2017-03-07 | A kind of preparation method of surfactant-modified fuel battery anode catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111151237A (en) * | 2020-01-20 | 2020-05-15 | 云南电网有限责任公司电力科学研究院 | Preparation method of noble metal catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489904A (en) * | 2016-01-13 | 2016-04-13 | 山东星火科学技术研究院 | Preparation method for anode catalyst of methanol fuel cell |
-
2017
- 2017-03-07 CN CN201710131845.8A patent/CN106898785A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489904A (en) * | 2016-01-13 | 2016-04-13 | 山东星火科学技术研究院 | Preparation method for anode catalyst of methanol fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| HUI CHEN,ET AL.: ""Ethanol oxidation on Pd/C promoted with CaSiO3 in alkaline medium"", 《ELECTROCHIMICA ACTA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111151237A (en) * | 2020-01-20 | 2020-05-15 | 云南电网有限责任公司电力科学研究院 | Preparation method of noble metal catalyst |
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