KR101938333B1 - Preparation method of cubic platinum nanoparticles for ammonia oxidtion - Google Patents
Preparation method of cubic platinum nanoparticles for ammonia oxidtion Download PDFInfo
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- KR101938333B1 KR101938333B1 KR1020160130047A KR20160130047A KR101938333B1 KR 101938333 B1 KR101938333 B1 KR 101938333B1 KR 1020160130047 A KR1020160130047 A KR 1020160130047A KR 20160130047 A KR20160130047 A KR 20160130047A KR 101938333 B1 KR101938333 B1 KR 101938333B1
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- platinum
- platinum nanoparticles
- present
- reducing agent
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 83
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 28
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- -1 borohydride Chemical compound 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 claims description 3
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims 2
- 235000010323 ascorbic acid Nutrition 0.000 claims 1
- 239000011668 ascorbic acid Substances 0.000 claims 1
- 229960005070 ascorbic acid Drugs 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 23
- 239000003381 stabilizer Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 7
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000013078 crystal Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/023—
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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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B22F1/0044—
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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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
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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
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
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- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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
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Abstract
본 발명은암모니아 산화반응용 정방형 백금 나노입자의 제조방법에 관한 것으로, 보다 상세하게는 표면 안정제를 사용하지 않고, 암모니아 산화반응 활성이 뛰어난 정방형 백금 나노입자를 제조하는 방법을 제공할 수 있으며, 이를 이용하여 성능이 우수한 직접 암모니아 연료전지의 촉매로 응용할 수 있다.The present invention relates to a method for producing a tetragonal platinum nanoparticle for ammonia oxidation reaction, and more particularly, to a method for preparing a tetragonal platinum nanoparticle excellent in ammonia oxidation reaction activity without using a surface stabilizer. Can be applied as a catalyst of a direct ammonia fuel cell having excellent performance.
Description
본 발명은 암모니아 산화반응용 정방형 백금 나노입자의 제조방법에 관한 것으로, 보다 상세하게는 표면 안정제를 사용하지 않고, 암모니아 산화반응용 정방형 백금 나노입자를 제조하고, 이를 이용하여 직접 암모니아 연료전지용 촉매로 응용하는 기술에 관한 것이다.
More particularly, the present invention relates to a method for producing a square platinum nanoparticle for ammonia oxidation reaction without using a surface stabilizer, It relates to applied technology.
알칼리형 연료전지는 전해질로서 KOH, NaOH와 같은 알칼리 용액을 사용하는 연료전지로서, 수소와 산소가 만나 물과 전기를 발생시키는 전기화학적 에너지 변환장치이다. 다른 연료전지와 마찬가지로 친환경적이고, 에너지 변환효율이 높다는 많은 장점이 있지만, 전해질이 이산화탄소와 반응하여 염을 생성하기 때문에 연료로써 순수한 수소와 산소만 사용이 가능하다. 이러한 문제를 해결하기 위하여 연구되고 있는 것이 직접암모니아 연료전지이다. An alkaline fuel cell is a fuel cell using an alkaline solution such as KOH or NaOH as an electrolyte, and is an electrochemical energy conversion device in which hydrogen and oxygen meet to generate water and electricity. As with other fuel cells, it is environmentally friendly and has many advantages of high energy conversion efficiency. However, since the electrolyte reacts with carbon dioxide to form salts, pure hydrogen and oxygen can be used as fuel. An ammonia fuel cell has been studied to solve this problem.
암모니아는 수소와 마찬가지로 친환경적인 에너지원으로 수소보다 폭발 범위가 좁고, 저압에서 액화가 가능하기 때문에 저장과 운반이 쉽다. 또한 암모니아 특유의 냄새로 인해 누출감지가 용이하고, 암모니아성 폐수를 활용할 경우 폐수 처리와 동시에 전기를 생산할 수 있다는 장점이 있다. 그러나 암모니아 산화반응은 수소 산화반응에 비해 반응이 매우 복잡하고 느리기 때문에 암모니아 산화반응에 대한 활성이 높은 촉매 개발이 필요하다. 암모니아 산화반응용 촉매에 대한 연구는 백금에 이리듐, 루테늄 등의 암모니아 산화반응에 대한 활성이 뛰어난 금속을 합금화하여 촉매를 합성하는 방법과 백금의 특정 결정면을 성장시켜 백금 입자를 구조적으로 제어하는 방법이 있다.Ammonia, like hydrogen, is an environmentally friendly energy source. Its range of explosion is narrower than that of hydrogen, and liquefaction at low pressure makes it easy to store and transport. In addition, it is easy to detect leakage due to the characteristic smell of ammonia, and when ammonia wastewater is utilized, it can produce electricity simultaneously with wastewater treatment. However, since ammonia oxidation reaction is very complicated and slower than hydrogen oxidation reaction, it is necessary to develop a catalyst having high activity for ammonia oxidation reaction. A study on the catalyst for ammonia oxidation reaction is a method of synthesizing a catalyst by alloying platinum with a metal having an excellent activity for oxidation reaction of ammonia such as iridium and ruthenium and a method of structurally controlling platinum particles by growing a specific crystal plane of platinum have.
백금의 여러 결정면 중 (100)면은 암모니아 산화에 우수한 활성을 나타내는 것으로 보고되고 있는데, 백금입자의 특정 결정면만을 성장시키기 위해서는 복잡한 공정과 표면 안정제가 필요하다. 표면 안정제를 사용할 경우 촉매 입자 표면에 강하게 흡착하여 결정성장을 제어하기 때문에 완전한 제거 어렵다. 표면 안정제가 제거되지 않고 촉매 표면에 남아있을 경우 촉매의 활성점을 점유하게 되어 성능 저하의 원인이 된다.
It has been reported that the (100) plane of platinum has excellent activity for ammonia oxidation. However, complex processes and surface stabilizers are required to grow only specific crystal faces of platinum particles. When a surface stabilizer is used, it is strongly adsorbed on the surface of the catalyst particles to control crystal growth, so that it is difficult to completely remove the surface stabilizer. If the surface stabilizer is not removed and remains on the surface of the catalyst, it occupies the active site of the catalyst, which is a cause of performance deterioration.
본 발명은 상기와 같은 문제점을 고려하여 안출된 것으로, 본 발명의 표면 안정제를 사용하지 않고, 암모니아 산화반응 활성이 뛰어난 정방형 백금 나노입자를 제조하는 방법을 제공하고자 하는 것이다.
SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a method for producing a square platinum nanoparticle excellent in ammonia oxidation reaction activity without using the surface stabilizer of the present invention.
상기한 바와 같은 목적을 달성하기 위한 본 발명의 일 측면은 백금 전구체, 환원제 및 반응 지연제를 혼합하여 반응시키는 단계;를 포함하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법에 관한 것이다.According to an aspect of the present invention, there is provided a method of preparing a platinum nanoparticle for ammonia oxidation, which comprises mixing and reacting a platinum precursor, a reducing agent, and a reaction retarder.
본 발명의 일 구현예에 따르면, 상기 백금 전구체의 형태는 아세틸아세토네이트염, 염화물, 브롬화물, 요오드화물, 질산염, 아질산염, 황산염, 아세트산염, 아황산염 및 수산화물 중에서 선택되는 1종 이상의 형태일 수 있다.According to an embodiment of the present invention, the form of the platinum precursor may be at least one form selected from an acetylacetonate salt, a chloride, a bromide, an iodide, a nitrate, a nitrite, a sulfate, an acetate, a sulfite and a hydroxide .
본 발명의 다른 구현예에 따르면, 상기 환원제는 디메틸포름아미드, 포름알데히드, 아세트알데히드, 글리옥살, 벤잘알데히드, 히드라진, 히드라진하이드레이트, 하이드록실아민, 테트라부틸암모늄, 보로하이드라이드, 탄닌산, 아스코르빈산, 아스코르빈산나트륨, 수소화붕소나트륨, 디메틸아민보란, 트리메틸아민보란, 구연산, 구연산나트륨, 디보란, 수소화리튬알루미늄, 글리콜, 글리세롤, 글루코스, 로첼염, 스트르산염, 포르말린 중에서 선택되는 1종 이상일 수 있다.According to another embodiment of the present invention, the reducing agent is selected from the group consisting of dimethylformamide, formaldehyde, acetaldehyde, glyoxal, benzaldehyde, hydrazine, hydrazine hydrate, hydroxylamine, tetrabutylammonium, borohydride, tannic acid, At least one member selected from the group consisting of sodium ascorbate, sodium borohydride, dimethylamine borane, trimethylamine borane, citric acid, sodium citrate, diborane, lithium aluminum hydride, glycol, glycerol, glucose, .
본 발명의 또 다른 구현 예에 따르면, 상기 반응 지연제는 아세틸아세톤, 빙초산, 에틸렌글라이콜, 트리에틸렌글라이콜 및 가수화된 물 중에서 선택되는 1종 이상일 수 있다.According to another embodiment of the present invention, the reaction retarder may be at least one selected from acetylacetone, glacial acetic acid, ethylene glycol, triethylene glycol, and hydrated water.
본 발명의 또 다른 구현예에 따르면, 상기 반응 지연제는 아세틸아세톤인 것이 바람직하다.According to another embodiment of the present invention, the reaction retarder is preferably acetylacetone.
본 발명의 또 다른 구현예에 따르면, 상기 환원제 및 반응 지연제의 부피비는 1 : 0.01-0.5일 수 있다. According to another embodiment of the present invention, the volume ratio of the reducing agent and the reaction retarder may be 1: 0.01-0.5.
본 발명의 또 다른 구현 예에 따르면, 백금 전구체 및 환원제의 몰비는 1 : 3000-6500 일 수 있다.According to another embodiment of the present invention, the molar ratio of the platinum precursor and the reducing agent may be 1: 3000-6500.
본 발명의 또 다른 구현예에 따르면, 상기 반응은 120 내지 200 ℃ 및 1 내지 3 기압에서 수행될 수 있다.According to another embodiment of the present invention, the reaction may be carried out at 120 to 200 ° C and 1 to 3 atm.
본 발명의 또 다른 구현예에 따르면, 상기 정방형 백금 나노입자의 크기는 1-50 nm일 수 있다.According to another embodiment of the present invention, the size of the square platinum nanoparticles may be 1-50 nm.
본 발명의 다른 측면은 본 발명에 따른 제조방법에 의해 제조된 정방형 백금 나노입자를 포함하는 직접 암모니아 연료전지용 촉매에 관한 것이다.Another aspect of the present invention relates to a catalyst for a direct ammonia fuel cell comprising square platinum nanoparticles produced by the process according to the present invention.
본 발명의 또 다른 측면은 상기 촉매를 포함하는 직접 암모니아 연료전지에 관한 것이다.
Another aspect of the present invention relates to a direct ammonia fuel cell comprising the catalyst.
본 발명에 따르면, 표면 안정제를 사용하지 않고, 암모니아 산화반응 활성이 뛰어난 정방형 백금 나노입자를 제조하는 방법을 제공할 수 있다.
According to the present invention, it is possible to provide a method for producing square platinum nanoparticles excellent in ammonia oxidation reaction activity without using a surface stabilizer.
도 1은 본 발명의 실시예 1로부터 합성된 정방형 백금 나노입자의 투과전자현미경(TEM) 이미지이다.
도 2는 본 발명의 비교예 1로부터 합성된 백금 나노입자의 투과전자현미경(TEM) 이미지이다.
도 3은 본 발명의 비교예 2로부터 합성된 백금 나노입자의 투과전자현미경(TEM) 이미지이다.
도 4는 본 발명의 실시예 1 및 비교예 1 내지 3의 백금 나노입자의, 황산 분위기 하에서 측정된 순환전류전압(cyclic voltammetry, CV) 곡선 그래프이다.
도 5는 본 발명의 실시예 1 및 비교예 1 내지 3의 백금 나노입자의, 반쪽전지 실험에서의 암모니아 산화성능을 나타낸 그래프이다.
도 6은 본 발명의 비교예 2의 상용의 백금 촉매의, 단위전지 실험에서의 전류-전압 및 전력 곡선을 나타낸 그래프이다.
도 7은 본 발명의 비교예 2로부터 합성된 백금 나노입자의, 단위전지 실험에서의 전류-전압 및 전력 곡선을 나타낸 그래프이다.
도 8은 본 발명의 실시예 1로부터 합성된 정방형 백금 나노입자의, 단위전지 실험에서의 전류-전압 및 전력 곡선을 나타낸 그래프이다.1 is a transmission electron microscope (TEM) image of the square platinum nanoparticles synthesized from Example 1 of the present invention.
2 is a transmission electron microscope (TEM) image of platinum nanoparticles synthesized from Comparative Example 1 of the present invention.
3 is a transmission electron microscope (TEM) image of platinum nanoparticles synthesized from Comparative Example 2 of the present invention.
4 is a cyclic voltammetry (CV) curve graph of the platinum nanoparticles of Example 1 of the present invention and Comparative Examples 1 to 3 measured under a sulfuric acid atmosphere.
5 is a graph showing the ammonia oxidation performance of the platinum nanoparticles of Example 1 of the present invention and Comparative Examples 1 to 3 in a half cell test.
6 is a graph showing the current-voltage and power curves of the conventional platinum catalyst of Comparative Example 2 of the present invention in the unit cell test.
7 is a graph showing the current-voltage and power curves of the platinum nanoparticles synthesized from Comparative Example 2 of the present invention in the unit cell experiment.
8 is a graph showing the current-voltage and power curves of the square platinum nanoparticles synthesized from Example 1 of the present invention in the unit cell experiment.
이하에서, 본 발명의 여러 측면 및 다양한 구현예에 대해 더욱 구체적으로 설명한다.In the following, various aspects and various embodiments of the present invention will be described in more detail.
본 발명의 일 측면은 백금 전구체, 환원제 및 반응 지연제를 혼합하여 반응시키는 단계;를 포함하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법에 관한 것이다.One aspect of the present invention relates to a method for preparing a square platinum nanoparticle for ammonia oxidation, which comprises mixing and reacting a platinum precursor, a reducing agent, and a reaction retarder.
종래의 직접 암모니아 연료전지 내 암모니아 산화반응용 백금 촉매의 경우, 우수한 산화 활성을 나타내는 Pt(100) 결정면의 성장을 위하여 올레일아민(oleylamine), 올레산(oleic acid), 세틸트리메틸암모늄브로마이드(cetyltrimethylammonium bromide, CTAB), 폴리비닐피롤리돈(polyvinylpyrrolidone, PVP) 등의 표면 안정제를 사용하여 백금 입자를 제조하였으며, 이 경우에는 표면 안정제가 백금 입자의 표면에 강하게 흡착하여 결정성장을 제어하기 때문에 완전한 제거가 어려우며, 이로 인하여 촉매의 활성점을 점유하게 되어 촉매의 성능 저하를 초래하였다. 또한, 상기 표면 안정제를 제거하는 단계가 추가되어, 제조공정이 복잡한 단점이 있었다. In the case of a platinum catalyst for ammonia oxidation reaction in a conventional direct ammonia fuel cell, oleylamine, oleic acid, cetyltrimethylammonium bromide (hereinafter, referred to as " cetyltrimethylammonium bromide " , CTAB), and polyvinylpyrrolidone (PVP). In this case, the surface stabilizer is strongly adsorbed on the surface of the platinum particles to control the crystal growth, And this leads to the occupation of the active sites of the catalyst, resulting in deterioration of catalyst performance. In addition, a step of removing the surface stabilizer is added, which has a disadvantage in that the production process is complicated.
본 발명에서는 반응 지연제를 사용하여, 백금 입자의 반응속도를 제어함으로써 백금의 결정면 성장을 제어하여 표면 안정제의 사용 없이도 정방형 구조의 백금 나노입자의 합성이 가능하도록 하였다. 특히, 백금 나노입자가 정방형을 이루게 되면 입자 표면에 Pt(100) 결정면이 노출되어, 입자 표면에서의 암모니아 산화반응이 일반적인 백금 나노입자에 비해 빠른 속도로 진행되어 연료전지의 성능을 향상시키는 효과가 있다. 또한, 반응 지연제를 사용할 경우에는 표면 안정제와는 다르게 화학 반응 평형으로 입자의 성장을 제어하기 때문에, 세척만으로도 쉽게 제거가 가능하여, 합성 시 추가 공정이 필요치 않다는 장점이 있다.In the present invention, by controlling the reaction rate of platinum particles by using a reaction retarder, the crystal growth of platinum is controlled to enable the synthesis of platinum nanoparticles having a square structure without using a surface stabilizer. Particularly, when the platinum nanoparticles are formed into a square, the Pt (100) crystal face is exposed on the particle surface, and the ammonia oxidation reaction on the particle surface progresses at a faster rate than the ordinary platinum nanoparticles, thereby improving the performance of the fuel cell have. In addition, when the reaction retarder is used, since the growth of the particles is controlled by the chemical reaction equilibrium unlike the surface stabilizer, it can be easily removed even by washing, and there is an advantage that no additional process is required in the synthesis.
본 발명의 일 구현예에 따르면, 상기 백금 전구체의 형태는 아세틸아세토네이트염, 염화물, 브롬화물, 요오드화물, 질산염, 아질산염, 황산염, 아세트산염, 아황산염 및 수산화물 중에서 선택되는 1종 이상의 형태일 수 있으며, 이에 한정되지 않는다. 구체적으로는 아세틸아세토네이트염 형태를 사용할 수 있다.According to an embodiment of the present invention, the form of the platinum precursor may be at least one form selected from an acetylacetonate salt, a chloride, a bromide, an iodide, a nitrate, a nitrite, a sulfate, an acetate, a sulfite and a hydroxide , But is not limited thereto. Specifically, an acetylacetonate salt form can be used.
본 발명의 다른 구현예에 따르면, 상기 환원제는 디메틸포름아미드, 포름알데히드, 아세트알데히드, 글리옥살, 벤잘알데히드, 히드라진, 히드라진하이드레이트, 하이드록실아민, 테트라부틸암모늄, 보로하이드라이드, 탄닌산, 아스코르빈산, 아스코르빈산나트륨, 수소화붕소나트륨, 디메틸아민보란, 트리메틸아민보란, 구연산, 구연산나트륨, 디보란, 수소화리튬알루미늄, 글리콜, 글리세롤, 글루코스, 로첼염, 스트르산염, 포르말린 중에서 선택되는 1종 이상일 수 있으며, 이에 한정되지 않는다. 구체적으로는 디메틸포름아미드을 사용할 수 있다.According to another embodiment of the present invention, the reducing agent is selected from the group consisting of dimethylformamide, formaldehyde, acetaldehyde, glyoxal, benzaldehyde, hydrazine, hydrazine hydrate, hydroxylamine, tetrabutylammonium, borohydride, tannic acid, At least one member selected from the group consisting of sodium ascorbate, sodium borohydride, dimethylamine borane, trimethylamine borane, citric acid, sodium citrate, diborane, lithium aluminum hydride, glycol, glycerol, glucose, But is not limited thereto. Specifically, dimethylformamide can be used.
본 발명의 또 다른 구현예에 따르면, 상기 반응 지연제는 아세틸아세톤, 빙초산, 에틸렌글라이콜, 트리에틸렌글라이콜, 및 가수화된 물 중에서 선택되는 1종 이상일 수 있으며, 이에 한정되지 않는다. 구체적으로 아세틸아세톤을 사용할 수 있다.According to another embodiment of the present invention, the reaction retarder may be at least one selected from acetylacetone, glacial acetic acid, ethylene glycol, triethylene glycol, and hydrated water, but is not limited thereto. Specifically, acetylacetone can be used.
본 발명의 또 다른 구현예에 따르면, 상기 환원제 및 반응 지연제의 부피비는 1 : 0.01-0.5일 수 있다. According to another embodiment of the present invention, the volume ratio of the reducing agent and the reaction retarder may be 1: 0.01-0.5.
특히, 상기 반응 지연제로 아세틸아세톤을 사용함과 동시에, 환원제 및 반응 지연제의 부피비가 상기 범위일 경우에는 Pt(100) 결정면만이 노출됨을 확인하였다, 반면 상기 반응 지연제로 아세틸아세톤이 아닌 다른 종류의 반응 지연제를 사용하거나, 상기 반응 지연제로 아세틸아세톤이 아닌 다른 종류의 반응 지연제를 사용함과 동시에, 환원제 및 반응 지연제의 부피비가 상기 범위를 벗어나는 경우에는 Pt(100) 결정면이 아닌 다른 결정면이 노출되어, 암모니아 산화 성능이 현저히 저하됨을 확인하였다.In particular, when acetyl acetone was used as the reaction retarder and the volume ratio of the reducing agent and the reaction retarder was in the above range, it was confirmed that only the Pt (100) crystal plane was exposed. On the other hand, When a reaction retarder is used or a reaction retarder other than acetylacetone is used as the reaction retarder and the volume ratio of the reducing agent and the reaction retarder is out of the range, a crystal plane other than the Pt (100) crystal plane is used And the ammonia oxidation performance was significantly lowered.
본 발명의 또 다른 구현 예에 따르면, 백금 전구체 및 환원제의 몰비는 1 : 3000-6500 일 수 있다.According to another embodiment of the present invention, the molar ratio of the platinum precursor and the reducing agent may be 1: 3000-6500.
본 발명의 또 다른 구현예에 따르면, 상기 반응은 120 내지 200 ℃ 및 1 내지 3 기압에서 수행될 수 있다.According to another embodiment of the present invention, the reaction may be carried out at 120 to 200 ° C and 1 to 3 atm.
본 발명의 또 다른 구현예에 따르면, 상기 정방형 백금 나노입자의 크기는 1-50 nm일 수 있다. 바람직하게는 5-10 nm일 수 있다.According to another embodiment of the present invention, the size of the square platinum nanoparticles may be 1-50 nm. Preferably 5-10 nm.
본 발명의 다른 측면은 본 발명에 따른 제조방법에 의해 제조된 정방형 백금 나노입자를 포함하는 직접 암모니아 연료전지용 촉매에 관한 것이다.Another aspect of the present invention relates to a catalyst for a direct ammonia fuel cell comprising square platinum nanoparticles produced by the process according to the present invention.
본 발명의 또 다른 측면은 상기 촉매를 포함하는 직접 암모니아 연료전지에 관한 것이다.Another aspect of the present invention relates to a direct ammonia fuel cell comprising the catalyst.
이하에서는 본 발명에 따른 제조예 및 실시예를 첨부된 도면과 함께 구체적으로 설명한다.
Hereinafter, production examples and embodiments according to the present invention will be described in detail with reference to the accompanying drawings.
실시예 1: 정방형 백금 나노입자의 합성Example 1: Synthesis of square platinum nanoparticles
백금 아세틸아세토네이트 0.0393 g, 디메틸포름아미드 41.6 ml 및 아세틸아세톤 8.4 ml를 혼합한 후, 오토클레이브 내의 닫힌계에서 1 기압, 160 ℃의 조건으로 36 시간 동안 반응시켜 백금 나노입자를 합성한 후, 원심분리를 통하여 분리 및 세척하고, 이소프로필알코올에 분산시킨 형태로 정방형 백금 나노입자를 얻었다.
0.0393 g of platinum acetylacetonate, 41.6 ml of dimethylformamide and 8.4 ml of acetylacetone were mixed and reacted in a closed system in an autoclave at 1 atm and 160 ° C for 36 hours to synthesize platinum nanoparticles, followed by centrifugation , And was dispersed in isopropyl alcohol to obtain square platinum nanoparticles.
비교예 1Comparative Example 1
상기 실시예 1과 동일하게 실시하되, 아세틸아세톤을 제외하여 백금 나노입자를 합성하였다.
Platinum nanoparticles were prepared in the same manner as in Example 1 except that acetylacetone was removed.
비교예 2Comparative Example 2
상기 실시예 1과 동일하게 실시하되, 아세틸아세톤 대신 폴리비닐피롤리돈(polyvinylpyrrolidone, PVP)를 사용하여 백금 나노입자를 합성하였다.
Platinum nanoparticles were prepared in the same manner as in Example 1 except that polyvinylpyrrolidone (PVP) was used instead of acetylacetone.
비교예 3Comparative Example 3
상용의 백금 촉매(Platinum black, Premeteck Co.)를 준비하였다.
A commercially available platinum catalyst (Platinum black, Premeteck Co.) was prepared.
도 1은 본 발명의 실시예 1로부터 합성된 정방형 백금 나노입자의 투과전자현미경(TEM) 이미지이다. 도 1을 참조하면, 본 발명의 제조방법에 따라 반응 지연제를 사용하여 제조된 백금 나노입자는 정방형 구조로 균일하게 합성되었으며, 그 크기는 5-10 nm이고, 격자 분석 결과 Pt(100)면이 노출된 형태로 성장한 것을 확인할 수 있다.
1 is a transmission electron microscope (TEM) image of the square platinum nanoparticles synthesized from Example 1 of the present invention. Referring to FIG. 1, platinum nanoparticles prepared using the reaction retarder according to the present invention were uniformly synthesized in a square structure, and the size thereof was 5-10 nm. As a result of the lattice analysis, And it was found that the plant was grown in the exposed form.
도 2는 본 발명의 비교예 1로부터 합성된 백금 나노입자의 투과전자현미경(TEM) 이미지이다. 도 2를 참조하면, 반응 지연제를 사용하지 않고 환원제만을 사용하여 제조된 백금 나노입자는 정방형 구조가 아닌, 다각형 구조로 합성되었고, 그 크기는 5-10 nm 정도 이며, 격자 분석 결과 백금의 다양한 결정면이 노출된 형태임을 확인할 수 있다.
2 is a transmission electron microscope (TEM) image of platinum nanoparticles synthesized from Comparative Example 1 of the present invention. Referring to FIG. 2, platinum nanoparticles prepared using only a reducing agent without using a reaction retarder were synthesized into a polygonal structure rather than a square structure. The size of the platinum nanoparticles was about 5-10 nm. As a result of the lattice analysis, It can be confirmed that the crystal face is exposed.
도 3은 본 발명의 비교예 2로부터 합성된 백금 나노입자의 투과전자현미경(TEM) 이미지이다. 도 3을 참조하면, 표면 안정제를 사용하여 합성한 백금 나노입자는 정방형 구조로 잘 제어되어 있으며, 그 입자 크기는 10-15 nm임을 확인할 수 있다.
3 is a transmission electron microscope (TEM) image of platinum nanoparticles synthesized from Comparative Example 2 of the present invention. Referring to FIG. 3, platinum nanoparticles synthesized using a surface stabilizer are well controlled in a square structure, and the particle size is 10-15 nm.
도 4는 본 발명의 실시예 1 및 비교예 1 내지 3의 백금 나노입자의, 황산 분위기 하에서 측정된 순환전류전압(cyclic voltammetry, CV) 곡선 그래프이다. 도 4를 참조하면, 백금 나노입자들의 황산에 대한 백금의 결정면에 따른 특성 피크를 확인할 수 있다. 실시예 1의 경우 Pt(100)면 특성피크에 해당하는 0.27 V에서 뾰족한 피크와 0.3-0.4 V 사이에서의 산화 피크가 관찰되는 것으로 보아 Pt(100)면이 발달한 정방형 구조임을 확인할 수 있다.
4 is a cyclic voltammetry (CV) curve graph of the platinum nanoparticles of Example 1 of the present invention and Comparative Examples 1 to 3 measured under a sulfuric acid atmosphere. Referring to FIG. 4, characteristic peaks of platinum nanoparticles according to the crystal plane of platinum against sulfuric acid can be confirmed. In the case of Example 1, it can be confirmed that a sharp peak at 0.27 V corresponding to the characteristic peak of Pt (100) plane and an oxidation peak between 0.3-0.4 V are observed, indicating that the Pt (100) plane has a developed square structure.
도 5는 본 발명의 실시예 1 및 비교예 1 내지 3의 백금 나노입자의, 반쪽전지 실험에서의 암모니아 산화성능을 나타낸 그래프이다. 도 5에서 볼 수 있듯이, 0.2 V 부근에서 측정된 산화 전류의 값을 비교해보면, 실시예 1의 정방형 백금 나노입자는 1.30 mA, 비교예 1의 백금 나노입자는 0.34 mA, 비교예 3의 상용 백금 촉매는 0.13 mA로 각각 측정되었으며, 비교예 2의, 표면 안정제를 사용하여 합성한 백금 나노입자의 경우 산화전류가 매우 낮게 측정되었다. 실시예 1의 정방형 백금 나노입자의 경우 반쪽전지 조건에서 비교예 1의 백금 나노입자 대비 약 4 배, 비교예 3의 상용 백금 촉매 대비 10 배 우수한 암모니아 산화 성능을 나타냄을 확인할 수 있다. 비교예 2의 백금 나노입자는 구조 제어는 이루어졌으나, 표면 활성점을 표면 안정제가 둘러싸고 있기 때문에 성능이 매우 낮음을 확인할 수 있다.
5 is a graph showing the ammonia oxidation performance of the platinum nanoparticles of Example 1 of the present invention and Comparative Examples 1 to 3 in a half cell test. As can be seen from FIG. 5, when the values of the oxidation current measured at around 0.2 V were compared, the square platinum nanoparticles of Example 1 were 1.30 mA, the platinum nanoparticles of Comparative Example 1 were 0.34 mA, The catalyst was measured at 0.13 mA, and the oxidation current of platinum nanoparticles synthesized using the surface stabilizer of Comparative Example 2 was measured to be very low. It can be seen that the square platinum nanoparticles of Example 1 exhibit excellent ammonia oxidation performance in quasi-platinum nanoparticles of about 4 times compared to the platinum nanoparticles of Comparative Example 1 and 10 times of the commercial platinum catalyst of Comparative Example 3. [ The platinum nanoparticles of Comparative Example 2 were controlled in structure, but the performance was very low because the surface stabilizer surrounds the surface active sites.
도 6은 본 발명의 비교예 3의 상용의 백금 촉매의, 단위전지 실험에서의 전류-전압 및 전력 곡선을 나타낸 그래프이다. 도 6을 참조하면, 상용 백금 촉매의 최대 전력 밀도는 18 mW/cm2로 측정되었다.6 is a graph showing the current-voltage and power curves of a commercially available platinum catalyst of Comparative Example 3 of the present invention in the unit cell test. Referring to FIG. 6, the maximum power density of the commercial platinum catalyst was measured to be 18 mW / cm 2 .
도 7은 본 발명의 비교예 1로부터 합성된 백금 나노입자의, 단위전지 실험에서의 전류-전압 및 전력 곡선을 나타낸 그래프이다. 도 7을 참조하면, 비교예 1의 구조가 제어되지 않고 합성된, 백금 입자의 최대 전력 밀도는 27.6 mW/cm2로 나타났다.7 is a graph showing the current-voltage and power curves of the platinum nanoparticles synthesized from Comparative Example 1 of the present invention in the unit cell experiment. Referring to FIG. 7, the maximum power density of platinum particles synthesized without controlling the structure of Comparative Example 1 was 27.6 mW / cm 2 .
도 8은 본 발명의 실시예 1로부터 합성된 정방형 백금 나노입자의, 단위전지 실험에서의 전류-전압 및 전력 곡선을 나타낸 그래프이다. 도 8을 참조하면 실시예 1로부터 합성된 정방형 백금 나노입자의 최대 전력 밀도는 39.1 mW/cm2임을 확인 할 수 있다. 8 is a graph showing the current-voltage and power curves of the square platinum nanoparticles synthesized from Example 1 of the present invention in the unit cell experiment. Referring to FIG. 8, the maximum power density of the square platinum nanoparticles synthesized from Example 1 is 39.1 mW / cm 2 .
상기 도 6, 7 및 8에서의 백금 촉매의 단위전지 성능을 비교해 보면, 실시예 1의 백금 촉매의 성능은 비교예 3의 상용의 백금 촉매 대비 약 2.2 배, 비교예 1의 구조가 제어되지 않은 백금입자는 상용의 백금 촉매에 대비 약 1.5 배로 높게 나타나, 본 발명에 따른 제조방법으로 제조된 정방형 백금 나노입자는 상용의 백금 촉매에 비하여 현저히 우수한 단위전지 성능을 갖음을 확인할 수 있다.6, 7, and 8, the performance of the platinum catalyst of Example 1 was about 2.2 times that of the commercial platinum catalyst of Comparative Example 3, and the structure of Comparative Example 1 was not controlled Platinum particles were about 1.5 times higher than those of conventional platinum catalysts. It can be seen that the square platinum nanoparticles prepared by the production method according to the present invention have remarkably excellent unit cell performance as compared with commercially available platinum catalysts.
그러므로 본 발명에 따르면, 표면 안정제를 사용하지 않고, 암모니아 산화반응 활성이 뛰어난 정방형 백금 나노입자를 제조하는 방법을 제공할 수 있으며, 이를 이용하여 성능이 우수한 직접 암모니아 연료전지의 촉매로 응용할 수 있다.Therefore, according to the present invention, it is possible to provide a method for producing a square platinum nanoparticle excellent in ammonia oxidation reaction activity without using a surface stabilizer, and can be applied as a catalyst of a direct ammonia fuel cell having excellent performance.
Claims (11)
상기 반응 지연제는 아세틸아세톤이고,
상기 환원제 및 반응 지연제의 부피비는 1 : 0.01-0.5인 것을 특징으로 하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법.A step of mixing the platinum precursor, the reducing agent and the reaction retarder, and reacting the platinum precursor, the reducing agent, and the reaction retarder,
Wherein said reaction retardant is acetylacetone,
Wherein the volume ratio of the reducing agent and the reaction retarder is 1: 0.01-0.5.
상기 백금 전구체의 형태는 아세틸아세토네이트염, 염화물, 브롬화물, 요오드화물, 질산염, 아질산염, 황산염, 아세트산염, 아황산염 및 수산화물 중에서 선택되는 1종 이상의 형태인 것을 특징으로 하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법.The method according to claim 1,
Wherein the form of the platinum precursor is at least one type selected from an acetylacetonate salt, a chloride, a bromide, an iodide, a nitrate, a nitrite, a sulfate, an acetate, a sulfite and a hydroxide. / RTI >
상기 환원제는 디메틸포름아미드, 포름알데히드, 아세트알데히드, 글리옥살, 벤잘알데히드, 히드라진, 히드라진하이드레이트, 하이드록실아민, 테트라부틸암모늄, 보로하이드라이드, 탄닌산, 아스코르빈산, 아스코르빈산나트륨, 수소화붕소나트륨, 디메틸아민보란, 트리메틸아민보란, 구연산, 구연산나트륨, 디보란, 수소화리튬알루미늄, 글리콜, 글리세롤, 글루코스, 로첼염, 스트르산염, 포르말린 중에서 선택되는 1종 이상인 것을 특징으로 하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법.The method according to claim 1,
The reducing agent may be selected from the group consisting of dimethylformamide, formaldehyde, acetaldehyde, glyoxal, benzaldehyde, hydrazine, hydrazine hydrate, hydroxylamine, tetrabutylammonium, borohydride, tannic acid, ascorbic acid, sodium ascorbate, sodium borohydride , At least one selected from the group consisting of dimethylamine borane, trimethylamine borane, citric acid, sodium citrate, diborane, lithium aluminum hydride, glycol, glycerol, glucose, A method for producing platinum nanoparticles.
상기 백금 전구체 및 환원제의 몰비는 1 : 3000-6500인 것을 특징으로 하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법.The method according to claim 1,
Wherein the molar ratio of the platinum precursor and the reducing agent is 1: 3000-6500.
상기 반응은 120 내지 200 ℃ 및 1 내지 3 기압에서 수행되는 것을 특징으로 하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법.The method according to claim 1,
Wherein the reaction is carried out at a temperature of 120 to 200 ° C and a pressure of 1 to 3 atm.
상기 정방형 백금 나노입자의 크기는 1-50 nm인 것을 특징으로 하는 암모니아 산화반응용 정방형 백금 나노입자의 제조방법.The method according to claim 1,
Wherein the size of the square platinum nanoparticles is 1-50 nm.
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