JP2017087151A - 金属ナノクラスター触媒 - Google Patents
金属ナノクラスター触媒 Download PDFInfo
- Publication number
- JP2017087151A JP2017087151A JP2015221482A JP2015221482A JP2017087151A JP 2017087151 A JP2017087151 A JP 2017087151A JP 2015221482 A JP2015221482 A JP 2015221482A JP 2015221482 A JP2015221482 A JP 2015221482A JP 2017087151 A JP2017087151 A JP 2017087151A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- catalyst
- dendrimer
- oxidation reaction
- sub
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 81
- 239000002184 metal Substances 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000000412 dendrimer Substances 0.000 claims abstract description 48
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 150000002739 metals Chemical class 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 23
- 239000010931 gold Substances 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002837 carbocyclic group Chemical group 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002923 metal particle Substances 0.000 abstract description 10
- 230000002776 aggregation Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 5
- 230000001603 reducing effect Effects 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 239000011859 microparticle Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000003197 catalytic effect Effects 0.000 description 17
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 10
- 150000002466 imines Chemical class 0.000 description 10
- 150000002736 metal compounds Chemical class 0.000 description 8
- -1 lithium aluminum hydride Chemical compound 0.000 description 7
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 230000009918 complex formation Effects 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910018883 Pt—Cu Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004696 coordination complex Chemical group 0.000 description 2
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical group C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910016551 CuPt Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 1
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000012679 convergent method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012678 divergent method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- YIAPLDFPUUJILH-UHFFFAOYSA-N indan-1-ol Chemical compound C1=CC=C2C(O)CCC2=C1 YIAPLDFPUUJILH-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002366 time-of-flight method Methods 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
(2)サブナノ金属粒子を
(3)酸化反応の活性触媒成分とする
(4)金属ナノクラスター触媒である。
白金(Pt)、パラジウム(Pb)、ロジウム(Rh)、ルテニウム(Ru)、イリジウム(Ir)、金(Au)、銀(Ag)が考慮される。また、貴金属以外の金属としては、例えば、Cu(銅)、Cd(カドニウム)、Mg(マグネシウム)、Mn(マンガン)、Al(アルミニウム)、Sn(スズ)、Fe(鉄)、Ni(ニッケル)、Ti(チタン)、Nb(ニオブ)、V(バナジウム)、Bi(ビスマス)、Ga(ガリウム)等が例示される。なかでも、酸化反応への活性の観点からは、例えば、Cu、Zn、Al、Sn、Fe、Ti、Mn等が好ましく考慮される。後述の実施例にも例示したが、2種の貴金属とそれ以外の1種の金属との三元系の触媒構成としてAu(金)−Pt(白金)−銅(Cu)の金属ナノクラスター触媒が例示される。
x=4〜12
y=8〜16
z=32〜48
の範囲を例示することができる。鋳型としてのデンドリマーに、フェニルメタンコアのフェニルアゾメンG4デンドリマーを用いた場合には、例えば、x+y+z=60の範囲において、Au12Pt16Cu32のものが優れた触媒活性を示すことが確認されている。
式(I)の符号R2は、置換基を1つ以上有していてもよいフェニル基であり、全てが同一のものであっても互いに異なっていてもよい。置換基を有するフェニル基R2の具体例としては、ハロゲン原子、アルキル基、アルコキシ基、フェニル基、アミノ基、シアノ基またはジメチルアミノ基などの置換基がo位、m位、p位のいずれか1ヶ所または2ヶ所以上に置換した置換フェニル基が挙げられる。
3種以上の異種金属の本発明のサブナノ粒子の形成においては、この錯形成の段階において、デンドリマーにおける一部のイミン部位に1種の金属化合物が配位し、他のイミン部位に他種金属化合物を配位させることができる。たとえば、最初にイミン部位を有するフェニルアゾメチンデンドリマーに1種の金属化合物を滴下することで錯形成させ、次いで他種の金属化合物を順次に滴下することで錯形成させることにより好適に得ることができる。
公知の方法に従って合成したテトラフェニルメタンコアのフェニルアゾメチンG4デンドリマー(TPMG4デンドリマー)に対し、図1に示した模式図のように、12モル当量のAuCl3溶液、16モル当量のPtCl4溶液、32モル当量のCuCl2溶液を順次に加えて錯形成を行った。図2は、錯形成のプロセスについて、Au、Pt、Cuの集積ステップにともなう光吸収と波長との相関の変化を示している。
酸素圧:1atm
反応温度:90℃
触媒量:3.36mg
反応時間:0.5〜6時間
反応では、インダン中に触媒を添加し、酸素雰囲気下に攪拌した。
<実施例2>
次の反応式
<実施例3>
次の反応式
Claims (10)
- 3種以上の異種金属の合金を含むサブナノ金属粒子を酸化反応の活性触媒成分とすることを特徴とする金属ナノクラスター触媒。
- 前記異種金属は、貴金属を含むことを特徴とする請求項1に記載の金属ナノクラスター触媒。
- 前記異種金属は、少くとも2種の貴金属を含むことを特徴とする請求項1または2に記載の金属ナノクラスター触媒。
- 前記貴金属は、白金、パラジウム、ロジウム、ルテニウム、イリジウム、金および銀のうちのいずれかであることを特徴とする請求項2または3に記載の金属ナノクラスター触媒。
- 前記異種金属は、銅、亜鉛、アルミニウム、スズ、鉄、チタン、およびマンガンのうちの少くともいずれかを含むことを特徴とする請求項1から4のうちのいずれか一項に記載の金属ナノクラスター触媒。
- 前記異種金属は、Au(金)−Pt(白金)−Cu(銅)の三元系であることを特徴とする請求項2から5のうちのいずれか一項に記載の金属ナノクラスター触媒。
- 前記サブナノ金属粒子は、デンドリマーまたはハイパーブランチポリマーに保持されていることを特徴とする請求項1から6のうちのいずれか一項に記載の金属ナノクラスター触媒。
- 前記サブナノ金属粒子は、粒径が0.8〜1.8nmの範囲内にあることを特徴とする請求項1から7のうちのいずれか一項に記載の金属ナノクラスター触媒。
- 前記酸化反応は、炭化水素化合物の空気または酸素酸化反応であることを特徴とする請求項1から8のうちのいずれか一項に記載の金属ナノクラスター触媒。
- 前記炭化水素化合物は、炭素環を有する炭化水素化合物であることを特徴とする請求項9に記載の金属ナノクラスター触媒。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015221482A JP2017087151A (ja) | 2015-11-11 | 2015-11-11 | 金属ナノクラスター触媒 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015221482A JP2017087151A (ja) | 2015-11-11 | 2015-11-11 | 金属ナノクラスター触媒 |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2017087151A true JP2017087151A (ja) | 2017-05-25 |
Family
ID=58767268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015221482A Pending JP2017087151A (ja) | 2015-11-11 | 2015-11-11 | 金属ナノクラスター触媒 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2017087151A (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018145172A (ja) * | 2017-03-01 | 2018-09-20 | 国立大学法人東京工業大学 | 4種以上の異種金属塩化合物を精密集積したデンドリマーの異種金属塩集積体とサブナノ金属粒子の製造方法 |
CN111185169A (zh) * | 2020-01-14 | 2020-05-22 | 上海华谊(集团)公司 | 用于(甲基)丙烯酸酯生产的纳米金催化剂的制备方法 |
CN111408346A (zh) * | 2020-04-09 | 2020-07-14 | 中冶华天工程技术有限公司 | 一种磁性锰氧化物负载活性炭吸附催化材料快速制备方法 |
CN111564640A (zh) * | 2020-05-15 | 2020-08-21 | 中自环保科技股份有限公司 | 一种纳米结构可控的电催化剂合成方法 |
CN113117724A (zh) * | 2021-04-26 | 2021-07-16 | 安徽大学 | 一种可回收负载型Au52Cu72(SR)55团簇催化剂及其应用 |
CN114790216A (zh) * | 2022-03-09 | 2022-07-26 | 山西大学 | 红色荧光银纳米团簇及其制备方法和应用 |
CN115041236A (zh) * | 2022-07-25 | 2022-09-13 | 安徽大学 | 一种负载型Au-Ag纳米团簇催化剂及其在酮炔基化反应中的应用 |
US11452992B2 (en) * | 2019-03-20 | 2022-09-27 | King Fahd University Of Petroleum And Minerals | Iron oxide supported rhodium catalyst for nitroarene reduction |
CN115807244A (zh) * | 2023-02-09 | 2023-03-17 | 四川大学 | 一种铜修饰的钌纳米团簇催化材料及其制备方法和用途 |
CN116393128A (zh) * | 2023-04-11 | 2023-07-07 | 安庆长宏科技股份有限公司 | 一种石墨烯负载铜纳米簇的催化剂及其制备工艺 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005526596A (ja) * | 2002-03-16 | 2005-09-08 | シュトゥディエンゲゼルシャフト・コーレ・ミット・ベシュレンクテル・ハフツング | 水溶性ナノ分散金属酸化物コロイドをそのままで固定する方法 |
JP2008100987A (ja) * | 2006-09-11 | 2008-05-01 | Univ Of Tokyo | フェニルアゾメチンデンドリマー金属錯体とロジウム系ナノ微粒子並びにその触媒 |
JP2011056379A (ja) * | 2009-09-09 | 2011-03-24 | Toyota Motor Corp | 排ガス浄化触媒及びその製造方法 |
-
2015
- 2015-11-11 JP JP2015221482A patent/JP2017087151A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005526596A (ja) * | 2002-03-16 | 2005-09-08 | シュトゥディエンゲゼルシャフト・コーレ・ミット・ベシュレンクテル・ハフツング | 水溶性ナノ分散金属酸化物コロイドをそのままで固定する方法 |
JP2008100987A (ja) * | 2006-09-11 | 2008-05-01 | Univ Of Tokyo | フェニルアゾメチンデンドリマー金属錯体とロジウム系ナノ微粒子並びにその触媒 |
JP2011056379A (ja) * | 2009-09-09 | 2011-03-24 | Toyota Motor Corp | 排ガス浄化触媒及びその製造方法 |
Non-Patent Citations (2)
Title |
---|
TAKAHASHI MASAKI, ET AL.: "Reactivity Control of Multimetallic Sub-nanocluster Catalysts for Oxidation Reactions", 日本化学会第95春季年会(2015) 講演予稿集I, JPN6019017348, 11 March 2015 (2015-03-11), pages 59, ISSN: 0004165744 * |
小泉宙夢、他: "多元素からなる精密サブナノクラスターの酸化反応触媒活性", 日本化学会第95春季年会(2015) 講演予稿集II, JPN6019017347, 11 March 2015 (2015-03-11), pages 416, ISSN: 0004165743 * |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018145172A (ja) * | 2017-03-01 | 2018-09-20 | 国立大学法人東京工業大学 | 4種以上の異種金属塩化合物を精密集積したデンドリマーの異種金属塩集積体とサブナノ金属粒子の製造方法 |
US11452992B2 (en) * | 2019-03-20 | 2022-09-27 | King Fahd University Of Petroleum And Minerals | Iron oxide supported rhodium catalyst for nitroarene reduction |
US11712680B2 (en) | 2019-03-20 | 2023-08-01 | King Fahd University Of Petroleum And Minerals | Process for reducing aromatic nitro compounds with supported catalyst |
CN111185169A (zh) * | 2020-01-14 | 2020-05-22 | 上海华谊(集团)公司 | 用于(甲基)丙烯酸酯生产的纳米金催化剂的制备方法 |
CN111185169B (zh) * | 2020-01-14 | 2023-02-03 | 上海华谊(集团)公司 | 用于(甲基)丙烯酸酯生产的纳米金催化剂的制备方法 |
CN111408346A (zh) * | 2020-04-09 | 2020-07-14 | 中冶华天工程技术有限公司 | 一种磁性锰氧化物负载活性炭吸附催化材料快速制备方法 |
CN111564640A (zh) * | 2020-05-15 | 2020-08-21 | 中自环保科技股份有限公司 | 一种纳米结构可控的电催化剂合成方法 |
CN113117724A (zh) * | 2021-04-26 | 2021-07-16 | 安徽大学 | 一种可回收负载型Au52Cu72(SR)55团簇催化剂及其应用 |
CN113117724B (zh) * | 2021-04-26 | 2023-09-08 | 安徽大学 | 一种可回收负载型Au52Cu72(SR)55团簇催化剂及其应用 |
CN114790216A (zh) * | 2022-03-09 | 2022-07-26 | 山西大学 | 红色荧光银纳米团簇及其制备方法和应用 |
CN114790216B (zh) * | 2022-03-09 | 2023-09-22 | 山西大学 | 红色荧光银纳米团簇及其制备方法和应用 |
CN115041236A (zh) * | 2022-07-25 | 2022-09-13 | 安徽大学 | 一种负载型Au-Ag纳米团簇催化剂及其在酮炔基化反应中的应用 |
CN115041236B (zh) * | 2022-07-25 | 2024-02-13 | 安徽大学 | 一种负载型Au-Ag纳米团簇催化剂及其在酮炔基化反应中的应用 |
CN115807244A (zh) * | 2023-02-09 | 2023-03-17 | 四川大学 | 一种铜修饰的钌纳米团簇催化材料及其制备方法和用途 |
CN116393128A (zh) * | 2023-04-11 | 2023-07-07 | 安庆长宏科技股份有限公司 | 一种石墨烯负载铜纳米簇的催化剂及其制备工艺 |
CN116393128B (zh) * | 2023-04-11 | 2023-08-15 | 安庆长宏科技股份有限公司 | 一种石墨烯负载铜纳米簇的催化剂及其制备工艺 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2017087151A (ja) | 金属ナノクラスター触媒 | |
Li et al. | Recent advances in the precise control of isolated single-site catalysts by chemical methods | |
Zhou et al. | Noble-metal based random alloy and intermetallic nanocrystals: syntheses and applications | |
Hu et al. | Core–shell catalysts of metal nanoparticle core and metal–organic framework shell | |
Chang et al. | The tunable and highly selective reduction products on Ag@ Cu bimetallic catalysts toward CO2 electrochemical reduction reaction | |
Yamamoto et al. | Precision synthesis of subnanoparticles using dendrimers as a superatom synthesizer | |
Carenco et al. | Metal-dependent interplay between crystallization and phosphorus diffusion during the synthesis of metal phosphide nanoparticles | |
Hong et al. | Ultrathin free‐standing ternary‐alloy nanosheets | |
Mohl et al. | Formation of CuPd and CuPt bimetallic nanotubes by galvanic replacement reaction | |
Arandiyan et al. | Highly selective reduction of carbon dioxide to methane on novel mesoporous Rh catalysts | |
Sun et al. | Three-shell Cu@ Co@ Ni nanoparticles stabilized with a metal–organic framework for enhanced tandem catalysis | |
Xu et al. | Facile construction of N-doped graphene supported hollow PtAg nanodendrites as highly efficient electrocatalysts toward formic acid oxidation reaction | |
Cao et al. | Immobilization of ultrafine bimetallic Ni–Pt nanoparticles inside the pores of metal–organic frameworks as efficient catalysts for dehydrogenation of alkaline solution of hydrazine | |
Li et al. | Light-induced selective hydrogenation over PdAg nanocages in hollow MOF microenvironment | |
Volosskiy et al. | Metal-organic framework templated synthesis of ultrathin, well-aligned metallic nanowires | |
Qi et al. | Enhancing the CO2-to-CO conversion from 2D silver nanoprisms via superstructure assembly | |
JP2011089143A (ja) | 一元系及び二元系の立方体型金属ナノ粒子の製造方法 | |
JP5794294B2 (ja) | 金属粒子及びそれを含む排ガス浄化用触媒並びにそれらの製造方法 | |
Xu et al. | Spherical sandwich Au@ Pd@ UIO-67/Pt@ UIO-n (n= 66, 67, 69) core–shell catalysts: Zr-based metal–organic frameworks for effectively regulating the reverse water–gas shift reaction | |
WO2017103492A2 (fr) | Nanoparticules de carbure de fer, procédé pour leur préparation et leur utilisation pour la production de chaleur | |
Zhang et al. | Ordered PdCu-Based Core–Shell Concave Nanocubes Enclosed by High-Index Facets for Ethanol Electrooxidation | |
Yang et al. | Ethanol electrooxidation catalyzed by tungsten core@ palladium shell nanoparticles | |
Chalgin et al. | Manipulation of electron transfer between Pd and TiO2 for improved electrocatalytic hydrogen evolution reaction performance | |
Huang et al. | Atomic platinum skin under synergy of cobalt for enhanced methanol oxidation electrocatalysis | |
Chen et al. | Demonstration of controlled hydrogen release using Rh@ GQDs during hydrolysis of NH3BH3 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A80 | Written request to apply exceptions to lack of novelty of invention |
Free format text: JAPANESE INTERMEDIATE CODE: A80 Effective date: 20151210 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20181011 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190426 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190522 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190719 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20191101 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20191101 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20191203 |