CN103055893B - Supported cobalt platinum superlattices alloy nano particle composite catalyst and preparation method thereof - Google Patents
Supported cobalt platinum superlattices alloy nano particle composite catalyst and preparation method thereof Download PDFInfo
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- CN103055893B CN103055893B CN201210569087.5A CN201210569087A CN103055893B CN 103055893 B CN103055893 B CN 103055893B CN 201210569087 A CN201210569087 A CN 201210569087A CN 103055893 B CN103055893 B CN 103055893B
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Abstract
The invention discloses and a kind ofly carry cobalt platinum superlattices alloy nano particle Catalysts and its preparation method for the carbon of oxygen reduction reaction in alkalescence or acid medium, catalyst of the present invention has L1
2type superlattice structure.This catalyst has very high electro catalytic activity and stability to oxygen reduction reaction in alkalescence or acid medium, significantly reduces the consumption of noble metal platinum, has the advantage of low cost concurrently.
Description
Technical field
The invention belongs to technical field of energy material, be specifically related to a kind of supported cobalt platinum superlattices alloy nano particle composite catalyst being applied to redox reactions and preparation method thereof.
Background technology
Oxygen reduction reaction is one of most important reaction in contemporary industry field, is reaction indispensable in various fuel cell, metal-air battery, the process of sewage electroxidation, chemical industry electrolysis field.Due to the dynamic process that redox reactions is slower, therefore, need efficient oxygen reduction reaction catalyst to promote oxygen reduction reaction acceleration.Oxygen reduction catalyst mainly contains noble metal and alloy catalyst, metal oxide and metallo-chelate catalyst.At present, the Pt/C catalyst of business is the most frequently used oxygen reduction electro-catalyst, has the advantage of active height and good stability.But Pt/C catalyst is expensive, and cost is high, limit its further application in the industry.In addition, the electrochemistry poor durability of Pt/C catalyst in highly acid or strongly basic medium, chemical property decay is serious, can not meet the needs of the medium-term and long-term stable operation of actual industrial production.For above commercial Application problem, people are currently suggested multiple solution: one is by the size Control of platinum and alloy particle thereof at 2 ~ 10nm, to give full play to the excellent hydrogen reduction electro catalytic activity of metal platinum; Two is loaded to by platinum on the larger material with carbon element of specific area, improves the hydrogen reduction catalytic performance of unit mass platinum; Three is the electro-chemical activities significantly being improved noble metal catalyst by precious metal alloys method.Make platinum and other metallic alloying activity and durability that can not only improve Pt/C catalyst, significantly reduce the consumption of platinum simultaneously, thus significantly reduce the cost of catalyst, save valuable Pt resource.Therefore, the alloying of noble metal is to improve the activity of noble metal oxygen reduction eelctro-catalyst and durability is one of focus of research at present.
Summary of the invention
The object of the invention is to solve that oxygen reduction electro-catalyst activity is low, poor durability, and the problem such as production cost is high, a kind of efficient, inexpensive eelctro-catalyst being applicable to oxygen reduction reaction and preparation method thereof is provided.In order to realize object of the present invention, intend adopting following technical scheme:
One aspect of the present invention relates to a kind of carbon and carries cobalt platinum superlattices alloy nano particle catalyst, it is characterized in that in described catalyst X-ray diffractogram, 2 θ have 23.1 ± 0.1
o, 32.9 ± 0.1
o, 53.1 ± 0.1
owith 58.6 ± 0.1
ocharacteristic peak; Preferably, described carbon is carbon black.
In a preferred embodiment of the present invention, the mass ratio of cobalt platinum is between 1:13 to 1:1.
In a preferred embodiment of the present invention, the mass ratio of cobalt platinum and carbon carrier is between 1:5 to 1:2.
In another preferred embodiment of the present invention, the particle diameter of described cobalt platinum is between 4-10nm.
The present invention also relates to the preparation method of above-mentioned catalyst on the other hand, and it comprises the steps:
(1) ethylene glycol solution of cobalt chloride hexahydrate and chloroplatinic acid is put into the ethylene glycol containing carbon carrier, ultrasonic more than 10min, regulate the above-mentioned pH value containing glycol reaction system to 8-10, be preferably between 8.5-9.5, pulverize 90-120 time with 1400-1800W power in ultrasonic disintegrator, obtain black slurries, at 30 ~ 90 DEG C, under being preferably 70 ~ 90 DEG C of stirring states, drip NaBH
4solution, and react 2 ~ 4h at such a temperature, finally filtered by slurries, deionized water is washed, dry, obtains the cobalt nano platinum particle/carbon matrix precursor powder with certain alloying level;
(2) preparation-obtained cobalt nano platinum particle/carbon matrix precursor powder is placed in alumina crucible; heat-treat under protective atmosphere: be raised to 600 ~ 1000 DEG C with the heating rate of 5 ~ 10 DEG C/min; and cool to sample with the furnace room temperature after constant temperature 0.5h ~ 1.5h at such a temperature, obtain carbon and carry cobalt platinum superlattices alloy catalyst.
In a preferred embodiment of the present invention, described carbon carrier is without chemically treated carbon black.
Carbon prepared by the present invention carries cobalt platinum superlattices alloy nano particle and has L12 type platinum cobalt superlattice structure, improves platinum and and the activity of alloy catalyst and durability.
Accompanying drawing explanation
Fig. 1: carbon prepared by embodiment carries the transmission electron microscope photo of platinum cobalt superlattices alloy catalyst, interior illustration is alloy particle transmission electron microscope photo, and alloy particle even height is dispersed in carbon support, and particle size is at 5 ~ 10nm.(wherein (a) prepares the transmission electron microscope photo that carbon carries platinum cobalt superlattices alloy catalyst for embodiment 1; B () prepares the transmission electron microscope photo that carbon carries platinum cobalt superlattices alloy catalyst for embodiment 2; C () prepares the transmission electron microscope photo that carbon carries platinum cobalt superlattices alloy catalyst for embodiment 3);
Fig. 2: carbon prepared by embodiment 1,2,3 carries the X-ray diffractogram of platinum cobalt superlattices alloy catalyst, can find out that the diffraction maximum of heat treatment rear catalyst and the diffraction maximum of L12 type CoPt3 match, illustrate and define superlattice structure;
Fig. 3: carbon prepared by embodiment 3 carries the rotating circular disk curve comparison figure of the hydrogen reduction of cobalt platinum superlattices alloy catalyst and business Pt/C (E-TEX) catalyst.The initial hydrogen reduction current potential of cobalt platinum superlattices alloy catalyst prepared is as seen from the figure suitable with business Pt/C (E-TEX) catalyst, and its current density is higher than commercial catalysts, has higher catalytic current.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
the ethylene glycol solution of the chloroplatinic acid of the cobalt chloride hexahydrate of 7.5mg and 9.3ml 0.01M is put into the 50ml ethylene glycol containing 100mg Vulcan XC-72 carbon black, ultrasonic 15min, above-mentioned system pH is regulated to be 9 by 1M NaOH solution, 99 times are pulverized with 1600W power in ultrasonic disintegrator, obtain black slurries, these slurries are put into flask, under 80 DEG C of stirring states, drips the NaBH of 10ml 0.6M
4solution, and react 3h at such a temperature, finally slurries are filtered, spend deionized water, dry, obtain black precursor powder.
by step
prepared precursor powder is placed in alumina crucible; heat-treat under protective atmosphere: be raised to 1000 DEG C with the heating rate of 8 DEG C/min; and cool to sample with the furnace room temperature after constant temperature 0.5h at such a temperature, obtaining platinum cobalt alloy ratio is that the carbon of 3:1 carries cobalt platinum superlattices alloy catalyst.
Embodiment 2
the ethylene glycol solution of the chloroplatinic acid of the cobalt chloride hexahydrate of 38.7mg and 5.4ml 0.01M is put into the 50ml ethylene glycol containing 100mg Vulcan XC-72 carbon black, ultrasonic 15min, above-mentioned system pH is regulated to be 9 by 1M NaOH solution, 99 times are pulverized with 1600W power in ultrasonic disintegrator, obtain black slurries, these slurries are put into flask, under 80 DEG C of stirring states, drips the NaBH of 10ml 1M
4solution, and react 3 hours at such a temperature, finally slurries are filtered, spend deionized water, dry, obtain the precursor powder of black.
by step
prepared precursor powder is placed in alumina crucible; heat-treat under protective atmosphere: be raised to 1000 DEG C with the heating rate of 9 DEG C/min; and cool to sample with the furnace room temperature after constant temperature 0.5h at such a temperature, obtaining platinum cobalt alloy ratio is that the carbon of 1:3 carries cobalt platinum superlattices alloy catalyst.
Embodiment 3
the ethylene glycol solution of the chloroplatinic acid of the cobalt chloride hexahydrate of 18.9mg and 7.9ml 0.01M is put into the 50ml ethylene glycol containing 100mg Vulcan XC-72 carbon black, ultrasonic 15min, above-mentioned system pH is regulated to be 9 with NaOH (1M) solution, 99 times are pulverized with 1600W power in ultrasonic disintegrator, obtain black slurries, these slurries are put into flask, under 80 DEG C of stirring states, drips the NaBH of 10ml 1.2M
4solution, and react 3h at such a temperature, finally slurries are filtered, spend deionized water, dry, obtain the precursor powder of black.
by step
prepared precursor powder is placed in alumina crucible; heat-treat under protective atmosphere: be raised to 1000 DEG C with the heating rate of 8 DEG C/min; and cool to sample with the furnace room temperature after constant temperature 0.5h at such a temperature, obtaining platinum cobalt alloy ratio is that the carbon of 1:1 carries cobalt platinum superlattices alloy catalyst.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any change of expecting without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (4)
1. carbon carries a cobalt platinum superlattices alloy nano particle catalyst, it is characterized in that, platinum cobalt superlattices alloy particle belongs to CoPt
3intermetallic compound, has L
12type superlattice structure; The mass ratio of cobalt platinum is between 1:13 to 1:1; The mass ratio of cobalt platinum and carbon carrier is between 1:5 to 1:2; The particle diameter of described cobalt platinum is between 4 ~ 10nm.
2. the preparation method of catalyst described in claim 1, it comprises the steps:
(1) ethylene glycol solution of cobalt chloride hexahydrate and chloroplatinic acid is put into the ethylene glycol containing carbon carrier, the mass ratio of water and ethylene glycol controls 3.1 ~ 3.3, ultrasonic more than 10min, regulate above-mentioned pH value to 8 ~ 10 containing glycol reaction system, pulverize 90 ~ 120 times with 1400 ~ 1800W power in ultrasonic disintegrator, obtain black slurries, under 30 ~ 90 DEG C of stirring states, drip NaBH
4solution, sodium borohydride quality is 32 ~ 52 with the ratio of the gross mass of slaine, and reacts 2 ~ 4h at such a temperature, is finally filtered by slurries, and deionized water is washed, dry, obtains the cobalt nano platinum particle/carbon matrix precursor powder with certain alloying level;
(2) preparation-obtained cobalt nano platinum particle/carbon matrix precursor powder is placed in alumina crucible; heat-treat under protective atmosphere: be raised to 600 ~ 1000 DEG C with the heating rate of 5 ~ 10 DEG C/min; and cool to sample with the furnace room temperature after constant temperature 0.5h ~ 1.5h at such a temperature, obtain carbon and carry cobalt platinum superlattices alloy catalyst.
3. method for preparing catalyst according to claim 2, is characterized in that dripping NaBH under 70 ~ 90 DEG C of stirring states
4solution.
4. the method for preparing catalyst according to Claims 2 or 3, described carbon carrier is without chemically treated carbon black.
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| CN105594035B (en) * | 2013-08-09 | 2018-07-06 | 日产自动车株式会社 | Catalyst granules and use its electrode catalyst, electrolyte film-electrode bond and fuel cell |
| CN104043453B (en) * | 2014-01-06 | 2015-12-09 | 北京化工大学 | A kind of support type cobaltosic oxide nano composite catalyst and application |
| CN104014810B (en) * | 2014-05-29 | 2016-08-17 | 燕山大学 | A kind of method utilizing octreotide acetate to prepare the spherical cobalt-platinum alloy of chain for template |
| CN104014811B (en) * | 2014-05-29 | 2016-03-02 | 燕山大学 | A kind of octreotide acetate that utilizes is for the method for Template preparation coralloid nano cobalt |
| CN104475126B (en) * | 2014-12-11 | 2017-10-20 | 北京化工大学 | Fuel cell carbon supported core-shell platinum cobalt platinum catalyst and preparation method thereof |
| CN104485463B (en) * | 2014-12-30 | 2017-01-04 | 西北师范大学 | A kind of alloy-oxide complex carbon material supported precious metal catalyst and preparation method thereof |
| CN105489907B (en) * | 2015-11-30 | 2018-02-13 | 北京化工大学 | A kind of carbon nanotube loaded platinum iron superlattices alloy nano particle and preparation method thereof |
| CN105413709B (en) * | 2015-12-11 | 2018-01-30 | 中国科学院上海高等研究院 | A kind of platinum cobalt nanometer bi-metal catalyst of more cubes of dendritic morphologies and its preparation method and application |
| CN108470920A (en) * | 2018-04-08 | 2018-08-31 | 北京化工大学 | A kind of graphene-supported platinum cobalt tungsten alloy nano-particle composite catalyst and preparation method thereof for acid medium |
| CN111224118A (en) * | 2019-11-15 | 2020-06-02 | 一汽解放汽车有限公司 | Multi-element doped platinum-based catalyst and preparation method and application thereof |
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| CN102277622A (en) * | 2011-07-22 | 2011-12-14 | 北京化工大学 | Copper-platinum superlattice alloy nano-tube and preparation method thereof |
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| CN102277622A (en) * | 2011-07-22 | 2011-12-14 | 北京化工大学 | Copper-platinum superlattice alloy nano-tube and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Co-alloying effect of Co and Cr with Pt for oxygen electro-reduction reaction;Min Ku Jeon et.al.;《Electrochimica Acta》;20120110;第64卷;第147-148页第2.1，2.2节，图1b * |
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