WO2016072755A1 - 담체-나노입자 복합체, 이의 제조방법, 및 이를 포함하는 촉매 - Google Patents
담체-나노입자 복합체, 이의 제조방법, 및 이를 포함하는 촉매 Download PDFInfo
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- WO2016072755A1 WO2016072755A1 PCT/KR2015/011814 KR2015011814W WO2016072755A1 WO 2016072755 A1 WO2016072755 A1 WO 2016072755A1 KR 2015011814 W KR2015011814 W KR 2015011814W WO 2016072755 A1 WO2016072755 A1 WO 2016072755A1
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 41
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
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- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 51
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- 239000002245 particle Substances 0.000 claims description 11
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- 229910002651 NO3 Inorganic materials 0.000 claims description 8
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- 150000004820 halides Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 6
- 239000003021 water soluble solvent Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
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- 239000012696 Pd precursors Substances 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
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- 239000003381 stabilizer Substances 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
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- 230000000694 effects Effects 0.000 description 10
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- 125000003277 amino group Chemical group 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
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- 229910052697 platinum Inorganic materials 0.000 description 5
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- 229910052739 hydrogen Inorganic materials 0.000 description 4
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 125000000879 imine group Chemical group 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- 101150003085 Pdcl gene Proteins 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 239000002526 disodium citrate Substances 0.000 description 1
- 235000019262 disodium citrate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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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
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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
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
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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
- B01J37/024—Multiple impregnation or coating
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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
- B01J37/12—Oxidising
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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
- B01J37/16—Reducing
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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
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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
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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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- 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
Definitions
- the present specification relates to a carrier-nanoparticle complex, a method for preparing the same, and a catalyst comprising the same.
- Nanoparticles are particles with nanoscale particle sizes, which are completely different from bulk materials due to their large specific surface area and quantum confinement effect, in which the energy required for electron transfer varies with the size of the material. , Electrical and magnetic properties. Therefore, because of these properties, much attention has been focused on its application in the field of catalysts, electromagnetism, optics, medicine and the like. Nanoparticles are intermediates between bulk and molecules, and are capable of synthesizing nanoparticles in terms of a two-way approach, a "top-down” approach and a “bottom-up” approach.
- Synthesis methods of metal nanoparticles include a method of reducing metal ions with a reducing agent in a solution, a method using gamma rays, and an electrochemical method, but conventional methods are difficult to synthesize nanoparticles having a uniform size and shape, or organic solvents.
- the economical mass production of high quality nanoparticles has been difficult due to various reasons, such as environmental pollution and high cost.
- the present specification is to provide a carrier-nanoparticle composite, a method for preparing the same, and a catalyst including the same, which can overcome the above problems.
- One embodiment of the present specification comprises the steps of forming a first solution comprising a water-soluble solvent, a precursor of a first metal, a precursor of a second metal and a carrier; Adding a first reducing agent to the first solution to form a core part including a first metal and a second metal; Adjusting the pH of the first solution to 8 or more between the forming of the first solution and the forming of the core part; After forming the core portion, adding a Pt precursor to the first solution to form a second solution; Adding a second reducing agent to the second solution to form a shell portion including Pt on at least a portion of the surface of the core portion; And adjusting the pH of the second solution to 8 or more between the forming of the second solution and the forming of the shell portion, wherein the carrier-nanoparticle complex having the core-shell nanoparticles supported thereon. It provides a method of manufacturing.
- An exemplary embodiment of the present specification provides a carrier-nanoparticle composite prepared by using the preparation method.
- An exemplary embodiment of the present disclosure provides a core shell nanoparticle including a core part including two different transition metals and a shell part including Pt formed on at least a portion of the surface of the core part; And a carrier on which the coreshell nanoparticles are supported, wherein at least a part of the surface of the carrier is coated with a polymer electrolyte including one or more functional groups including nitrogen, and the at least one coreshell nanoparticle is formed on the surface of the carrier. It provides a carrier-nanoparticle complex that is bonded to a nitrogen atom.
- One embodiment of the present specification provides a catalyst comprising the carrier-nanoparticle complex.
- the method for preparing a carrier-nanoparticle composite according to an exemplary embodiment of the present specification has an advantage of little environmental pollution using an aqueous solvent without using an organic solvent having a high risk of environmental pollution.
- the preparation method of the carrier-nanoparticle composite according to one embodiment of the present specification is performed in a low temperature atmosphere of 100 ° C. or less, and has an advantage of being able to manufacture a large amount at low cost.
- the method for preparing the carrier-nanoparticle composite according to one embodiment of the present specification does not use a surfactant, less toxic substances are generated during the manufacturing process, and the carrier-nanoparticle composite can be easily formed at low cost. There is this.
- Carrier-nanoparticle composite according to one embodiment of the present specification may be uniformly supported on the carrier core cell nanoparticles of a uniform size to implement a high catalytic activity.
- FIG. 1 and 2 show transmission electron microscope (TEM) images of the carrier-nanoparticle composite prepared according to Example 1.
- FIG. 1 and 2 show transmission electron microscope (TEM) images of the carrier-nanoparticle composite prepared according to Example 1.
- Figure 3 shows a high-angle annular dark-field (HADDF) image of the carrier-nanoparticle complex according to Example 1.
- HADDF high-angle annular dark-field
- FIG. 4 shows a transmission electron microscope (TEM) image of a carrier-nanoparticle composite prepared according to Reference Example 1.
- FIG. 4 shows a transmission electron microscope (TEM) image of a carrier-nanoparticle composite prepared according to Reference Example 1.
- Figure 5 shows a transmission electron microscope (TEM) image of the carrier-nanoparticle composite prepared according to Reference Example 2.
- FIG. 6 shows the results of energy dispersive spectroscopy (EDS) line scanning of the carrier-nanoparticle composite according to Example 1.
- EDS energy dispersive spectroscopy
- FIG. 7 shows cyclic voltammetry (CV) of the carrier-nanoparticle complexes according to Example 1 and Comparative Example 1.
- CV cyclic voltammetry
- FIG. 8 shows linear sweep voltammetry (LSV) of the carrier-nanoparticle complexes according to Example 1 and Comparative Example 1.
- LSV linear sweep voltammetry
- FIG. 9 is a result of measuring the performance of a single cell including a carrier-nanoparticle composite according to Example 1 and Comparative Example 1.
- FIG. 9 is a result of measuring the performance of a single cell including a carrier-nanoparticle composite according to Example 1 and Comparative Example 1.
- One embodiment of the present specification comprises the steps of forming a first solution comprising a water-soluble solvent, a precursor of a first metal, a precursor of a second metal and a carrier; Adding a first reducing agent to the first solution to form a core part including a first metal and a second metal; Adjusting the pH of the first solution to 8 or more between the forming of the first solution and the forming of the core part; After forming the core portion, adding a Pt precursor to the first solution to form a second solution; Adding a second reducing agent to the second solution to form a shell portion including Pt on at least a portion of the surface of the core portion; And adjusting the pH of the second solution to 8 or more between the forming of the second solution and the forming of the shell portion, wherein the carrier-nanoparticle complex having the core-shell nanoparticles supported thereon. It provides a method of manufacturing.
- the core shell nanoparticle may be provided with a shell portion including Pt on at least a part of the surface of the core portion including two kinds of metals.
- the core shell nanoparticle may include a shell part including Pt on the entire surface of the core part including two kinds of metals.
- the precursor of the present specification means a salt containing a metal ion.
- the precursor may be dissociated in a solvent to provide metal ions, and the metal ions may be reduced by a reducing agent to be a metal constituting the coreshell nanoparticle.
- the step of adjusting the pH of the first solution to 8 or more may be to adjust the pH to 8 or more and 13 or less. More specifically, adjusting the pH of the first solution to 8 or more may be to adjust the pH to 10.
- adjusting the pH of the second solution to 8 or more may be to adjust the pH to 8 or more and 13 or less. More specifically, adjusting the pH of the second solution to 8 or more may be to adjust the pH to 10.
- the surface of the core portion is negatively charged, so that the Pt precursor is easily located on the surface of the core portion to facilitate shell formation.
- the process of adjusting the pH may be adjusted by adding a base solution.
- a base solution selected from the group consisting of sodium hydroxide (NaOH), barium hydroxide (Ba (OH) 2 ), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) 2 ) and lithium hydroxide (LiOH) I can regulate it.
- the precursor of the first metal and the precursor of the second metal may be precursors of transition metals different from each other, and at least one may be a Pd precursor.
- the first metal may be a Pd precursor
- the second precursor may be a precursor of Co, Ni, Fe, or Cu.
- the precursor of the first metal and the precursor of the second metal, and the Pt precursor may be a water-soluble metal salt.
- the precursor of the first metal and the precursor of the second metal, and the Pt precursor may be ionized in an aqueous solvent.
- the manufacturing method according to an exemplary embodiment of the present specification is prepared using a water-soluble solvent and a water-soluble metal salt, there is no need to reduce or pyrolyze at a high temperature.
- the nanoparticles are prepared using a carbonyl-based metal precursor or an acetylacetonate-based metal precursor on an organic solvent, there is a problem in that a process of reducing and thermally decomposing under a high temperature of more than 100 ° C is required.
- the manufacturing method according to an exemplary embodiment of the present specification is relatively inexpensive and uses less water-soluble metal salts, thereby reducing management costs incurred in the manufacturing process.
- the first metal is Pd
- the second metal is ruthenium (Ru), molybdenum (Mo), vanadium (V), tungsten (W), cobalt (Co), iron (Fe) ), Selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), Cr (chromium), titanium (Ti), gold (Au), cerium (Ce), silver (Ag) or copper (Cu) May be).
- the precursor of the first metal is nitrate (Nitrate, NO 3 ⁇ ), halide (Halide), hydroxide (Hydroxide, OH ⁇ ) or sulfur oxide (Sulfate, SO) of the first metal 4 -),
- the precursor of the second metal is a nitrate (nitrate of the second metal, and NO 3 -), a halide (halide), hydroxide (hydroxide, OH -) or sulfur oxide (sulfate, SO 4 -) days Can be.
- the halide may be chloride (Chloride, Cl ⁇ ), bromide (Bomide, Br ⁇ ) or iodide (Iodide, I ⁇ ).
- the Pt precursor may be represented by the following formula (1).
- A is (NH 3 ), (CH 3 NH 2 ) or (H 2 O),
- n 2, 4 or 6
- n is an integer of any one of 1-7.
- the B is NO 3 -, NO 2 -, OH -, F -, Cl -, Br - or I - may be.
- the Pt precursor is Pt (NH 3 ) 4 (NO 3 ) 2 , Pt (NH 3 ) 4 Cl 2 , Pt (CH 3 NH 2 ) 4 (NO 3 ) 2 , Pt ( CH 3 NH 2 ) 4 Cl 2 , Pt (H 2 O) 4 (NO 3 ) 2 or Pt (H 2 O) 4 Cl 2 .
- the manufacturing method has an advantage that a process of supporting nanoparticles on a carrier is not necessary separately.
- the first solution includes a precursor of the first metal, a precursor of the second metal, and the carrier together to prepare a carrier-nanoparticle composite by a one-pot process, and thus does not require a separate supporting process.
- the carrier-nanoparticle composite is prepared by including the carrier together during the formation of the nanoparticles, there is an advantage in that adhesion and dispersion between the carrier and the nanoparticles are excellent.
- the adhesion between the carrier and the nanoparticles is excellent, there is an advantage that the durability can be improved because the interaction (interaction) between the nanoparticles and the carrier is improved.
- the dispersibility of the nanoparticles on the carrier is excellent, the active point that can participate in the reaction is increased, there is an effect that the reactivity is improved.
- the carrier may be a carbon-based carrier.
- the carbon-based carrier is carbon black, carbon nanotubes (CNT), graphite, graphite, graphene, activated carbon, mesoporous carbon, carbon fiber It may include one or more selected from the group consisting of (Carbon fiber) and carbon nano wire (Carbon nano wire).
- At least a part of the surface of the carrier may be coated with a polymer electrolyte including one or more functional groups including nitrogen.
- the functional group containing the nitrogen may be an amine group or an imine group.
- the polymer electrolyte may be substituted with at least one amine group or an imine group in a linear or branched hydrocarbon chain.
- At least one coreshell nanoparticle may be supported on the carbon-based carrier by combining with an amine group of the polymer electrolyte.
- the polymer electrolyte of the present specification may mean a polymer having a charge.
- the polymer electrolyte may be a synthetic polymer having an electric charge or an ion exchange resin.
- a polymer electrolyte including an amine group may be coated on one region of the surface of the carrier to induce bonding of the amine group and the coreshell nanoparticles. Accordingly, the aggregation phenomenon of the core shell nanoparticles may be alleviated, thereby increasing dispersibility of the core shell nanoparticles.
- the polymer electrolyte may include a polyallylamine hydrochloride (PAH) -based material or a polyethylene imine (PEI) -based material.
- PAH polyallylamine hydrochloride
- PEI polyethylene imine
- the forming of the core part may be performed at a temperature of 0 ° C. or more and 100 ° C. or less. Specifically, the step of forming the core portion may be performed at a temperature of more than 50 °C 75 °C.
- the forming of the shell part may be performed at room temperature.
- the normal temperature means a temperature in the range of 4 ° C to 35 ° C, more specifically 15 ° C to 28 ° C.
- the manufacturing method according to the exemplary embodiment of the present specification is performed at a low temperature condition of 100 ° C. or less, there is an advantage that high cost is not required to meet the process conditions.
- the water-soluble solvent may include water.
- the water-soluble solvent may be water or a mixture of water and an alcohol of C 1 -C 6 , and more specifically, may be water.
- the manufacturing method may not use a surfactant.
- the manufacturing method uses water as a solvent and does not use a surfactant, it has a cost-saving effect, which is advantageous in mass production, and is an environmentally friendly process.
- the surfactant since the surfactant surrounds the particle surface, there is a problem in that the reactant is not easily accessible when used in the catalytic reaction, and thus a post-process for removing the surfactant is required. Therefore, when the surfactant is not used, the process is simplified to reduce the cost, and is advantageous for mass production.
- the first solution may further include a stabilizer.
- the stabilizer may specifically include one or two or more selected from the group consisting of disodium phosphate, dipotassium phosphate, disodium citrate and trisodium citrate.
- the first reducing agent and the second reducing agent are each a strong reducing agent having a standard reduction of -0.23V or less, and have a reducing power capable of reducing dissolved metal ions to precipitate as metal particles. It is not limited.
- the first reducing agent and the second reducing agent may be at least one selected from the group consisting of NaBH 4 , NH 2 NH 2 , LiAlH 4 and LiBEt3H, respectively.
- the molar ratio of the precursor of the first metal and the precursor of the second metal may be 1: 1 to 1: 3.
- the number of moles of the Pt precursor may be 0.5 to 2 times the number of moles of the precursor of the first metal.
- An exemplary embodiment of the present specification provides a carrier-nanoparticle composite prepared by the preparation method.
- an exemplary embodiment of the present specification includes a core shell nanoparticle including a core part including two different transition metals and a shell part including Pt formed on at least a part of the surface of the core part; And it provides a carrier-nanoparticle composite prepared by the production method comprising a carrier on which the core-shell nanoparticles are supported.
- an exemplary embodiment of the present specification includes a core shell nanoparticle including a core part including two different transition metals and a shell part including Pt formed on at least a part of the surface of the core part; And a carrier on which the coreshell nanoparticles are supported, wherein at least a part of the surface of the carrier is coated with a polymer electrolyte including one or more functional groups including nitrogen, and the at least one coreshell nanoparticle is formed on the surface of the carrier. It provides a carrier-nanoparticle complex that is bonded to a nitrogen atom.
- the polymer electrolyte may be substituted with at least one amine group or an imine group in a linear or branched hydrocarbon chain.
- the polymer electrolyte may include a polyallylamine hydrochloride (PAH) -based material or a polyethylene imine (PEI) -based material.
- PAH polyallylamine hydrochloride
- PEI polyethylene imine
- At least one coreshell nanoparticle may be combined with a carrier by combining with a nitrogen atom of the polymer electrolyte.
- FIG. 6 shows the results of an energy dispersive spectroscopy (EDS) line scanning according to Example 1 of the present specification, in which Pt of the core shell nanoparticles and N positions of the polymer electrolyte overlap.
- each N contained in the polymer electrolyte may be combined with each coreshell nanoparticle, so that the coreshell nanoparticles may be evenly dispersed in the carrier.
- N and the core shell nanoparticles of the polymer electrolyte coated on the carrier are bonded to each other, so that the coreshell nanoparticles have high dispersibility and are supported on the carrier, and the coreshell It may mean that the high binding force of the nanoparticles and the carrier.
- the particle diameter of the core shell nanoparticles may be 1 nm or more and 10 nm or less. Specifically, according to one embodiment of the present specification, the particle diameter of the core-shell nanoparticles may be 3 nm or more and 6 nm or less.
- the total amount of the core shell nanoparticles may be 20 wt% or more and 50 wt% or less with respect to the carrier-nanoparticle composite.
- the carrier and the nanoparticles are as described above.
- One embodiment of the present specification provides a catalyst comprising the carrier-nanoparticle complex.
- the carrier-nanoparticle composite according to one embodiment of the present specification may generally be used to replace existing nanoparticles in the field where nanoparticles may be used.
- the carrier-nanoparticle composite according to one embodiment of the present specification has a very small size and a larger specific surface area than the conventional nanoparticles, and thus may exhibit excellent activity as compared with the conventional nanoparticles.
- the carrier-nanoparticle composite according to one embodiment of the present specification may be used in the field of catalysts.
- FIGS. 1 and 2 TEM images of the carrier-nanoparticle composite prepared according to Example 1 are shown in FIGS. 1 and 2.
- the carrier-nanoparticle composite prepared according to Example 1 can be seen that coreshell nanoparticles having a particle size of 3 nm to 6 nm are evenly distributed on the carrier.
- Figure 3 shows a high-angle annular dark-field (HADDF) image of the carrier-nanoparticle complex according to Example 1.
- HADDF high-angle annular dark-field
- Pt having a higher atomic number in HADDF is brighter than Pd. It can be seen that the nanoparticles of the carrier-nanoparticle composite according to Example 1 are core-shell nanoparticles including a shell portion including Pt. have.
- the component ratio of the core-shell nanoparticles of the carrier-nanoparticle composite according to Example 1 was 25.1 wt% of Pt, 14.43 wt% of Pd, and 2.45 wt% of Co. Analysis of the component ratio was used ICP equipment.
- FIG. 6 shows the results of energy dispersive spectroscopy (EDS) line scanning of the carrier-nanoparticle composite according to Example 1.
- EDS energy dispersive spectroscopy
- a carrier-nanoparticle complex was prepared in the same manner as in Example 1, except that the pH of the first solution was adjusted to 2.7.
- the TEM image of the carrier-nanoparticle composite prepared according to Reference Example 1 is shown in FIG. 4.
- a carrier-nanoparticle complex was prepared in the same manner as in Example 1, except that the pH of the first solution was adjusted to 7.
- the TEM image of the carrier-nanoparticle composite prepared according to Reference Example 2 is shown in FIG. 5.
- the dispersion degree is better than that in Reference Example 1, but it can be observed that the nanoparticles are partially aggregated.
- the treatment at the basic condition rather than the acid or neutral condition at the time of forming the core portion shows a higher degree of dispersion.
- the carrier-nanoparticle composite prepared according to Example 1 was applied as an electrode catalyst for a fuel cell cathode.
- Fuel cell catalyst evaluation was conducted in a half cell system.
- the electrode used a 3-electrode system, that is, a reference electrode, a counter electrode and a working electrode.
- the reference electrode was Ag / AgCl and the electrolyte was 0.5 M sulfuric acid solution. Or 0.1 M perchloric acid solution was used.
- cyclic voltammetry was used to scan 15 to 20 times from -0.2 V to 1.0 V, and the scan rate was 20 mV / s.
- the catalyst ink was prepared by mixing 2 mg of catalyst, 8 ⁇ l of 5% nafion, 1.6 mL of EtOH, and 0.4 mL of H 2 O, dispersed for 1 hour with an ultrasonic cleaner, and coating 20 ⁇ l on the RDE electrode and drying. .
- the amount of catalyst coated on the electrode was about 20 ⁇ g.
- the area of the electrode was 0.196 cm 2 .
- the 0.1 M perchloric acid solution was bubbled with pure oxygen for 30 minutes, and then circulated in the positive direction from the negative direction from 0.9 V to 0.4 V based on the normal hydrogen electrode (NHE) and the scan rate rate) is 20 mV / s and the rotating speed of the electrode was run at 1600 to 2500 RPM.
- FIG. 7 shows cyclic voltammetry (CV) of the carrier-nanoparticle complexes according to Example 1 and Comparative Example 1.
- FIG. 8 shows linear sweep voltammetry (LSV) of the carrier-nanoparticle complexes according to Example 1 and Comparative Example 1.
- LSV linear sweep voltammetry
- the catalyst was measured for oxygen reduction reaction (ORR) activity using 20 wt% and 46 wt% of Pt / C (carbon supported Pt) commercial catalyst and a carrier-nanoparticle composite prepared according to Example 1 above.
- ORR activity results are shown in Table 1 below.
- the carrier-nanoparticle composite according to Example 1 based on the Pt content was nearly twice as active per mass at 0.8 V as compared to the commercial catalyst.
- the carrier-nanoparticle composite according to Example 1 showed a higher degree of results than the conventional catalyst.
- electrochemically active surface area is about 35% superior to the commercial catalyst based on the Pt content. This result means that since Pt has a thin shell portion on the surface of the core portion, the surface area per Pt mass is formed to be wider than that of Pt particles, so that the activity per Pt mass is excellent.
- FIG. 9 is a result of measuring the performance of a single cell including the carrier-nanoparticle composite according to Example 1 and Comparative Example 1 as an electrode catalyst.
- the size of the membrane electrode assembly is 2.5 cm ⁇ 2.5 cm
- H 2 / Air is supplied under 100% humidification conditions, and the performance of a single cell was measured in an atmosphere of 80 °C, according to Example 1
- the sum of the masses of Pt and Pd per unit area of the carrier-nanoparticle composite was 0.2 mg / cm 2 .
- the performance of the unit cell including the carrier-nanoparticle complex according to Example 1 as an electrode catalyst was higher than that of the unit cell including the carrier-nanoparticle complex according to Comparative Example 1 as an electrode catalyst. It can be seen that the excellent performance.
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Abstract
Description
@0.8V | 실시예 1(25% Pt) | 상용촉매 1(20% Pt) | 상용촉매 2(46% Pt) |
ECSA(m2/g Pt) | 107.0 | 78.4 | 71.9 |
Mass Activity(A/g Pt) | 40.8 | 21.7 | 16.25 |
Mass Activity(A/g metal) | 24.6 | 21.7 | 16.25 |
Claims (24)
- 수용성 용매, 제1 금속의 전구체, 제2 금속의 전구체 및 담체를 포함하는 제1 용액을 형성하는 단계;상기 제1 용액에 제1 환원제를 첨가하여, 제1 금속 및 제2 금속을 포함하는 코어부를 형성하는 단계;상기 제1 용액을 형성하는 단계와 상기 코어부를 형성하는 단계 사이에, 상기 제1 용액의 pH를 8 이상으로 조절하는 단계;상기 코어부 형성 단계 이후, 상기 제1 용액에 Pt 전구체를 첨가하여 제2 용액을 형성하는 단계;상기 제2 용액에 제2 환원제를 첨가하여, 상기 코어부 표면의 적어도 일부에 Pt를 포함하는 쉘부를 형성하는 단계; 및상기 제2 용액을 형성하는 단계와 상기 쉘부를 형성하는 단계 사이에, 상기 제2 용액의 pH를 8 이상으로 조절하는 단계를 포함하는상기 담체에 코어쉘 나노입자가 담지된 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 제1 금속의 전구체 및 상기 제2 금속의 전구체는 서로 상이한 전이금속의 전구체이고, 적어도 하나는 Pd 전구체인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 제1 금속의 전구체 및 상기 제2 금속의 전구체, 및 상기 Pt 전구체는 수용성 금속염인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 제1 금속은 Pd이고,상기 제2 금속은 루테늄(Ru), 몰리브덴(Mo), 바나듐(V), 텅스텐(W), 코발트(Co), 철(Fe), 셀레늄(Se), 니켈(Ni), 비스무트(Bi), 주석(Sn), Cr(크롬), 타이타늄(Ti), 금(Au), 세륨(Ce), 은(Ag) 또는 구리(Cu)인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 제1 금속의 전구체는 상기 제1 금속의 질산화물(Nitrate, NO3 -), 할로겐화물(Halide), 수산화물(Hydroxide, OH-) 또는 황산화물(Sulfate, SO4 -)이고,상기 제2 금속의 전구체는 상기 제2 금속의 질산화물(Nitrate, NO3 -), 할로겐화물(Halide), 수산화물(Hydroxide, OH-) 또는 황산화물(Sulfate, SO4 -)인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 Pt 전구체는 하기 화학식 1로 표시되는 것인 담체-나노입자 복합체의 제조방법:[화학식 1]PtAmBn상기 화학식 1에 있어서,A는 (NH3), (CH3NH2) 또는 (H2O)이며,B는 1가의 음이온이고,m은 2, 4 또는 6이며,n은 1 내지 7 중 어느 하나의 정수이다.
- 청구항 6에 있어서,상기 B는 NO3 -, NO2 -, OH-, F-, Cl-, Br- 또는 I- 인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 담체는 탄소 기반의 담체인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 담체 표면의 적어도 일부는 질소를 포함하는 작용기를 1 이상 포함하는 고분자 전해질로 코팅된 것인 담체-나노입자 복합체의 제조방법.
- 청구항 9에 있어서,상기 고분자 전해질은 PAH(polyallylamine hydrochloride)계 물질 또는 PEI (polyethylene imine)계 물질을 포함하는 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 코어부를 형성하는 단계는 0 ℃ 이상 100 ℃ 이하의 온도에서 수행되는 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 쉘부를 형성하는 단계는 상온에서 수행되는 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 수용성 용매는 물을 포함하는 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 제1 용액은 안정화제를 더 포함하는 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 제1 금속의 전구체와 상기 제2 금속의 전구체의 몰비는 1:1 내지 1:3 인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1에 있어서,상기 Pt 전구체의 몰수는 제1 금속의 전구체 몰수의 0.5배 내지 2배인 것인 담체-나노입자 복합체의 제조방법.
- 청구항 1 내지 16 중 어느 한 항에 따른 제조방법을 이용하여 제조된 담체-나노입자 복합체.
- 2종의 서로 다른 전이금속을 포함하는 코어부, 상기 코어부 표면의 적어도 일부에 형성된 Pt를 포함하는 쉘부를 포함하는 코어쉘 나노입자; 및 상기 코어쉘 나노입자가 담지된 담체를 포함하고,상기 담체 표면의 적어도 일부는 질소를 포함하는 작용기를 1 이상 포함하는 고분자 전해질로 코팅되며,적어도 하나의 상기 코어쉘 나노입자는 상기 담체 표면의 질소 원자와 결합된 것인 담체-나노입자 복합체.
- 청구항 18에 있어서,상기 고분자 전해질은 PAH(polyallylamine hydrochloride)계 물질 또는 PEI (polyethylene imine)계 물질을 포함하는 것인 담체-나노입자 복합체.
- 청구항 18에 있어서,상기 담체-나노입자 복합체의 EDS 라인 스캐닝 결과, 코어쉘 나노입자의 Pt의 위치와 고분자 전해질의 N의 위치가 중첩되는 것인 담체-나노입자 복합체.
- 청구항 18에 있어서,상기 코어쉘 나노입자의 입경은 1 ㎚ 이상 10 ㎚ 이하인 것인 담체-나노입자 복합체.
- 청구항 18에 있어서,상기 코어쉘 나노입자의 함량은 상기 담체-나노입자 복합체에 대하여 20 중량% 이상 50 중량% 이하인 것인 담체-나노입자 복합체.
- 청구항 18에 있어서,상기 담체는 탄소 기반의 담체인 것인 담체-나노입자 복합체.
- 청구항 18 내지 23 중 어느 한 항에 따른 담체-나노입자 복합체를 포함하는 촉매.
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