KR101639724B1 - Composite particle for a catalyst and catalyst support and manufacturing method for the same - Google Patents
Composite particle for a catalyst and catalyst support and manufacturing method for the same Download PDFInfo
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- KR101639724B1 KR101639724B1 KR1020150108022A KR20150108022A KR101639724B1 KR 101639724 B1 KR101639724 B1 KR 101639724B1 KR 1020150108022 A KR1020150108022 A KR 1020150108022A KR 20150108022 A KR20150108022 A KR 20150108022A KR 101639724 B1 KR101639724 B1 KR 101639724B1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/002—Catalysts characterised by their physical properties
- B01J35/0073—Distribution of the active metal ingredient
- B01J35/0086—Distribution of the active metal ingredient egg-yolk like
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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
- B01J37/08—Heat treatment
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
Abstract
Description
The present invention relates to a composite particle which can be used as a catalyst itself and can also be used as a support for a catalyst, and more particularly to a composite particle comprising a transition metal- By forming a carbon-based shell having excellent crystallinity on the surface of the particles, it is possible to use the carbon-based shell as a catalyst itself, and also to increase the surface area of the carbon-based support excellent in crystallinity, The present invention relates to a composite particle which may increase durability and a method for producing the same.
The oxygen reduction reaction is a fundamental phenomenon of an energy conversion device through an electrochemical reaction such as a low-temperature fuel cell or a metal-air battery. The oxygen reduction reaction is a core-shell nano including platinum group pure metals, platinum alloys and platinum It is implemented through particles.
Further, although the catalyst is used as such, it is more preferable to use the catalyst dispersed on the surface of the support because the size of the catalyst particle can be reduced and the reaction surface area of the catalyst can be increased. Accordingly, the platinum catalyst has been used by being dispersed on a support of a carbon-based material such as graphite, denka black, ketjen black, acetylene black, carbon nanotube, carbon nanofiber, carbon nanowire, carbon nanoball or activated carbon.
For example, polymer electrolyte fuel cell catalysts are used in the form of Pt / C supported on platinum-made nano-sized carbon supports with high active area. The high anode potential, low pH, high oxygen concentration The carbon of the carbon support is oxidized in the form of CO or CO 2 in an equi-operation environment, and the active area of the platinum is also reduced, thereby deteriorating the performance of the fuel cell.
In order to solve these problems, a method has been proposed in which metal oxide particles are introduced onto the surface of a carbon support to enhance the durability of the carbon support (
In order to solve the problem of forming metal oxide particles, a method of forming a thin film of a stable graphite structure on a carbon support by using a chemical vapor deposition (CVD) method on the surface of a carbon support such as carbon black is proposed (Patent Document 3). This method has the advantage of obtaining a high purity quality at a relatively low cost, but has disadvantages of uniform dispersion and chemical gas generated during the process.
On the other hand, since platinum is an expensive material, it is increasingly necessary to realize an oxygen reduction reaction with a low-cost material as compared with platinum.
A material containing a transition metal can be used as a catalyst by causing an oxygen reduction reaction. Since the material containing a transition metal is low in durability, it is necessary to protect the material containing the transition metal with a material having excellent oxidation resistance such as graphite have.
For example, Fe 3 C particles and the Fe 3 graphite shell formed on the surface of the C particles of core-shell structure of the nano-composite particles, Fe constituting the core 3 C particles, the oxygen reduction reaction by a graphite shell and the electron transfer process And the graphite structure shell formed on the surface of the Fe 3 C particles can impart durability in an acidic and alkaline environment in which an oxygen reduction reaction occurs.
With regard to the synthesis of core-shell particles with a shell of stable graphite structure, a transition metal compound is synthesized so that a graphite shell is formed through a spray pyrolysis process using a gaseous precursor, and then a graphite shell A method of removing the non-formed transition metal compound particles can be used.
However, since the transition metal material thus synthesized has a complex structure of pure metal, carbide, and oxide, it is difficult to control the formation of the graphite shell in the synthesis process, and there is a limitation in controlling the superimposition and the amount of the support, .
The object of the present invention is to provide a composite particle which can be used not only as a catalyst for partially or wholly replacing platinum but also as a support for platinum by increasing the specific surface area of a carbonaceous material having excellent crystallinity.
Another object of the present invention is to provide a method for efficiently producing the composite particles.
According to an aspect of the present invention, there is provided a nanocomposite comprising: a carbon-based support; a plurality of nanoparticles composed of a material including a transition metal formed on the carbon-based support; and a carbon- To provide a composite particle.
According to another aspect of the present invention, there is provided a method of fabricating a nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite nanocomposite And then precipitating in a graphite phase on the surface of the nanoparticles to form a carbon-based shell.
The composite particles according to the present invention can be obtained by forming nanoparticles of a substance containing a transition metal on a carbon-based support and forming a carbon-based shell having a stable graphite structure on the surface of the nanoparticles, Can be remarkably improved and can be used as a catalyst for replacing a part or all of platinum.
Also, the composite particles according to the present invention have a large number of shells having a graphite structure having a good crystallinity on the carbon support, thereby increasing the surface area of the carbon support surface having excellent crystallinity, Can be suitably used also for a platinum group catalyst support since oxidation resistance can be greatly improved.
In addition, the method for preparing a composite particle according to the present invention comprises forming a plurality of nanoparticles composed of a substance containing a transition metal on a carbon-based support, It is possible to form a shell of a stable graphite structure having excellent durability and to control the thickness and the like of the graphite structure through the control of the heat treatment process and to manufacture the composite particles with high reliability at low cost.
1 is a schematic view of a composite particle according to an embodiment of the present invention.
FIG. 2 shows the C-Ni solubility versus C solubility according to temperature.
Fig. 3 is a view showing a process for producing a composite particle according to an embodiment of the present invention.
4 is a photograph of particles formed with nickel nanoparticles on the surface of carbon black particles.
5 is a photograph of the particles of FIG. 4 after subjected to low-temperature heat treatment.
Fig. 6 is a photograph of the particles of Fig. 4 after high-temperature heat treatment.
7 is a photograph showing the state after the composite particles according to the embodiment of the present invention are immersed in an acid solution for 24 hours and stirred.
8 shows the results of measurement of oxygen reduction reaction behavior of composite particles according to one embodiment of the present invention.
The singular forms used to describe the embodiments of the present invention are meant to include plural forms unless the phrases expressly mean the opposite. And includes meaning of specific characteristics, regions, integers, steps, and actions. Elements and / or components, and other particular features, regions, integers, steps, acts. Quot; does not exclude the presence or addition of elements, elements and / or groups.
Although not defined differently, all terms including technical terms and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Also, commonly used predefined terms are not to be construed as ideal or very formal meanings unless further defined and interpreted as having a meaning consistent with the relevant technical literature and the present disclosure.
As shown in FIG. 1, the composite particle according to the present invention comprises a carbon-based support, a plurality of nanoparticles composed of a material containing a transition metal formed on the carbon-based support, And a carbon-based shell of a graphite structure formed.
As the carbon-based support, at least one of carbon black, hollow graphitized carbon particles, carbon nanotubes, and carbon nanofibers can be preferably used, but is not limited thereto.
The transition metal-containing material may be any one selected from the group consisting of pure Fe, Fe alloy, Fe carbide, Co pure metal, Co alloy, Co carbide, Ni pure metal, Ni alloy, Ni carbide, But the present invention is not limited thereto, and other transition metals, alloys thereof or carbides thereof may be used depending on the use of the composite particles.
Meanwhile, in the present invention, 'nanoparticle' means particles having a particle size of less than 1000 nm.
Further, the carbon-based shell of the graphite structure may be made of a material having a graphite structure such as graphite or graphene, and may be doped with nitrogen.
The composite particles may be suitably used for a catalyst for a low-temperature fuel cell or a support for a catalyst, a catalyst for a secondary battery or a support for a catalyst, a drug delivery support, or the like.
The method for producing a composite particle according to the present invention includes the steps of forming nanoparticles composed of a substance containing a transition metal on the surface of a carbon-based support, and heating the nanostructured carbon- And precipitating the nanoparticles on the surface of the nanoparticles to form a carbon-based shell.
Since nanoparticles containing a transition metal are formed on the carbon support and the shell of the graphite structure is formed through the solidification and precipitation of carbon constituting the carbon support through the simple heat treatment, It is possible to form a shell that is easy to handle.
After forming the carbon-based shell, a step of removing nanoparticles having no graphite shell formed on the surface of the nanoparticles using an acidic solution may be further performed. Whereby when used as a catalyst or catalyst support, the reliability of the composite particles can be further enhanced.
Further, after the composite particles are synthesized, a step of further nitriding the composite particles may be performed. This makes it possible to improve the durability of the composite particles.
At this time, the nitriding process can be performed by depositing nitride with a target, or performing reactive vapor deposition in an environment containing nitrogen gas.
The nanoparticles made of a material containing the transition metal can be formed by a method of laminating a pure metal in a vacuum atmosphere or an inert atmosphere.
In addition, by controlling the heat treatment temperature differently, the size of the formed nanoparticles and the thickness of the shell of the formed graphite structure can be controlled in the heat treatment process.
[Example]
FIG. 2 shows the C solubility according to the temperature in the C-Ni binary phase. As shown in Fig. 2, Ni increases in the amount of C in a large amount as the temperature increases.
In this embodiment of the present invention, a composite particle having a graphite shell formed on Ni nanoparticles was prepared by using the solid solution of C on Ni.
FIG. 3 is a view showing a manufacturing process of a composite particle according to an embodiment of the present invention.
As shown in FIG. 3, first, nickel nanoparticles are formed on the hollow carbon black, and the carbon constituting the hollow carbon black is solidified in the nickel nanoparticles through heat treatment, and then the supersaturated carbon in the cooling process is nickel Precipitates on the surface of the nanoparticles, and a graphite shell is formed on the surface of the nickel nanoparticles in this process.
Specifically, nickel nanoparticles were synthesized on the surface of carbon black using a physical vapor deposition process in a nickel vapor phase while stirring carbon black nanoparticles of Cabot Co., The synthesis process
A voltage of 30 to 250 V and a capacity of 100 to 1,080 μF was applied to the carbon black by using nickel as a cathode electrode by using a vacuum arc plasma deposition apparatus and the pulse cycle was 5 to 25 Hz Were synthesized.
4 shows STEM-HADDF and TEM images of particles formed with nickel nanoparticles on the surface of carbon black particles, according to an embodiment of the present invention. As shown in FIG. 4, it can be seen that a large number of fine nickel nanoparticles having a size of several nm to several tens nm were formed on the surface of the carbon black through the above process.
Fig. 5 is a TEM image after synthesizing nickel nanoparticles on the surface of carbon black and then heat-treated at 450 캜 for 5 hours in an inert gas atmosphere or a vacuum atmosphere.
5, it was confirmed that a shell having a graphite structure excellent in crystallinity was formed on the surface of the nickel particles through a low-temperature heat treatment at 450 占 폚. Since this shell is not a separate carbon source supplied to the nickel nanoparticles from the outside, the carbon of the carbon support carbon black is dissolved in the nickel nanoparticles and precipitated on the surface thereof. In this process, the nickel nanoparticles are graphitized Catalyzed.
FIG. 6 is a graph showing the results of the synthesis of nickel nanoparticles on the surface of carbon black. The nickel nanoparticles were synthesized in an inert gas atmosphere or a vacuum atmosphere at a temperature of 350 to 550 ° C for 4 ≪ / RTI > after the heat treatment for 1 hour.
As shown in FIG. 6, when the heat treatment is performed at a relatively high temperature, the shell of the graphite structure is formed thicker than the low temperature heat treatment, which is a phenomenon caused by an increase in the amount of carbon.
As described above, the produced composite particles can remove nickel nanoparticles in which the shell is unstably formed using an acidic solution such as a sulfuric acid solution.
Nickel particles with unstable shells are also needed to prevent reliability degradation when composite particles are used as catalysts and to eliminate the deterioration of fuel cells or secondary batteries due to exposure of nickel when the composite particles are used as catalyst supports.
7 shows the composite particles prepared according to the embodiment of the present invention after stirring for 24 hours in a mixed acid solution in which a hydrochloric acid solution (8.642M) and a nitric acid solution (3.285M) are mixed.
As shown in FIG. 7, since a very stable graphite shell is formed on the surface of the nickel nanoparticles constituting the composite particles according to the embodiment of the present invention, the nickel particles having a stable shell are not dissolved in the sulfuric acid solution, As shown in FIG.
7, when the composite particles according to the embodiment of the present invention are used as a catalyst, they have excellent durability. For example, even when used as a support for a platinum catalyst, a fuel cell or a secondary battery It is expected that the deterioration problem will not occur.
On the other hand, the surface area of the shell of a stable graphite structure on the carbon support constituting the composite particles can be easily controlled through a method of increasing the size or density of the nickel nanoparticles.
8 shows the results of measurement of oxygen reduction reaction behavior of composite particles according to one embodiment of the present invention.
As shown in FIG. 8, as a result of the measurement of the oxygen reduction reaction, it was confirmed that the composite particles according to the example of the present invention exhibited the oxygen reduction reaction characteristics alone, and the composite particles according to the embodiment of the present invention It is expected that the reaction will have an effect on the activity.
Claims (12)
Forming a carbon-based shell by allowing a carbon component of the carbon-based support to be solidified on the surface of the nanoparticles after the carbon component is solid-dissolved in the nanoparticles through heat treatment.
Further, there is provided a method for producing a composite particle comprising the steps of: using an acidic solution to remove nanoparticles on which a graphite shell is not formed or unstably formed on the surface of said nanoparticles.
The method of producing composite particles according to claim 1, further comprising nitriding the composite particles.
Wherein the nanoparticles are formed by a method of depositing a pure metal in a vacuum atmosphere or an inert atmosphere by a physical vapor deposition method.
Wherein the heat treatment process controls the thickness of the shell layer formed through temperature control.
Wherein the nitriding treatment is performed by laminating a nitride target, or performing reactive vapor deposition in an environment containing nitrogen gas.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018067926A1 (en) * | 2016-10-07 | 2018-04-12 | Regents Of The University Of Minnesota | Iron-based nanoparticles and grains |
| KR20190112969A (en) * | 2018-03-27 | 2019-10-08 | 포항공과대학교 산학협력단 | Manufacturing method of core-shell composite particles |
| KR20220041501A (en) * | 2020-09-25 | 2022-04-01 | 현대제철 주식회사 | Catalyst for oxygen reduction reaction for secondary cell, proton exchange membrane fuel cell, and metal air cell having the same |
| KR20220078149A (en) | 2020-12-03 | 2022-06-10 | 한국과학기술연구원 | Method for preparing core-shell catalyst comprising platinum layer using surface hydrogen oxidation reaction |
| KR20230050677A (en) | 2021-10-08 | 2023-04-17 | 인천대학교 산학협력단 | Synthesis method of metal catalyst including carbon shell having controlled thickness via surface oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018067926A1 (en) * | 2016-10-07 | 2018-04-12 | Regents Of The University Of Minnesota | Iron-based nanoparticles and grains |
| US11161175B2 (en) | 2016-10-07 | 2021-11-02 | Regents Of The University Of Minnesota | Iron-based nanoparticles and grains |
| US11837393B2 (en) | 2016-10-07 | 2023-12-05 | Regents Of The University Of Minnesota | Iron-based nanoparticles and grains |
| KR20190112969A (en) * | 2018-03-27 | 2019-10-08 | 포항공과대학교 산학협력단 | Manufacturing method of core-shell composite particles |
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| KR20220041501A (en) * | 2020-09-25 | 2022-04-01 | 현대제철 주식회사 | Catalyst for oxygen reduction reaction for secondary cell, proton exchange membrane fuel cell, and metal air cell having the same |
| KR102517254B1 (en) * | 2020-09-25 | 2023-04-04 | 현대제철 주식회사 | Catalyst for oxygen reduction reaction for secondary cell, proton exchange membrane fuel cell, and metal air cell having the same |
| KR20220078149A (en) | 2020-12-03 | 2022-06-10 | 한국과학기술연구원 | Method for preparing core-shell catalyst comprising platinum layer using surface hydrogen oxidation reaction |
| KR20230050677A (en) | 2021-10-08 | 2023-04-17 | 인천대학교 산학협력단 | Synthesis method of metal catalyst including carbon shell having controlled thickness via surface oxidation |
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