JP2020127936A - ナノ結晶複合体 - Google Patents
ナノ結晶複合体 Download PDFInfo
- Publication number
- JP2020127936A JP2020127936A JP2020014377A JP2020014377A JP2020127936A JP 2020127936 A JP2020127936 A JP 2020127936A JP 2020014377 A JP2020014377 A JP 2020014377A JP 2020014377 A JP2020014377 A JP 2020014377A JP 2020127936 A JP2020127936 A JP 2020127936A
- Authority
- JP
- Japan
- Prior art keywords
- nanocrystal
- nanoparticles
- pieces
- metal oxide
- oxide
- 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
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 138
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 239000002105 nanoparticle Substances 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims description 51
- 150000004706 metal oxides Chemical class 0.000 claims description 51
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 30
- 238000006555 catalytic reaction Methods 0.000 claims description 25
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 24
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 24
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 230000000007 visual effect Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 38
- 239000013078 crystal Substances 0.000 description 33
- 230000003197 catalytic effect Effects 0.000 description 32
- 239000007789 gas Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 17
- 239000010949 copper Substances 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 11
- 125000004430 oxygen atom Chemical group O* 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910002528 Cu-Pd Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- -1 which is an oxide Chemical compound 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/04—Mixing
-
- 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
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/908—O2-storage component incorporated in the catalyst
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
Description
[1] 主表面および端面をもつ複数のナノ結晶片が相互に連結された連結集合体と、前記連結集合体に担持されたナノ粒子と、を備え、
前記複数のナノ結晶片のそれぞれが薄片状であり、
前記複数のナノ結晶片が前記主表面間に間隙を有し、
前記間隙が前記連結集合体の外側に開口して配置され、
前記ナノ粒子が前記複数のナノ結晶片とは異なる金属元素を有し、
前記複数のナノ結晶片の視野面積に対する前記ナノ粒子の視野面積の割合が2%以上50%以下であることを特徴とする、ナノ結晶複合体。
[2] 前記ナノ粒子の粒径が5nm以上100nm以下であり、かつ、
前記ナノ粒子が前記主表面に配置されている、上記[1]に記載のナノ結晶複合体。
[3] 前記複数のナノ結晶片が第一種金属酸化物であり、かつ、
前記ナノ粒子が前記第一種金属酸化物とは異なる第二種金属酸化物である、上記[1]又は[2]に記載のナノ結晶複合体。
[4] 前記第一種金属酸化物が酸化銅である、上記[3]に記載のナノ結晶複合体。
[5] 前記第二種金属酸化物が酸化セリウムナノ粒子又は酸化セリウムと酸化ジルコニウムとの混合体のナノ粒子である、上記[3]又は[4]に記載のナノ結晶複合体。
[6] 酸化還元触媒反応に使用するための上記[1]乃至[5]のいずれかに記載のナノ結晶複合体。
[7] 排気ガス浄化用触媒として使用するための上記[1]乃至[5]のいずれかに記載のナノ結晶複合体。
本発明に従うナノ結晶複合体は、主表面および端面をもつ複数のナノ結晶片が相互に連結された連結集合体と、該連結集合体上に担持されたナノ粒子とを備える。複数のナノ結晶片のそれぞれは薄片状であり、また、複数のナノ結晶片は主表面間に間隙を有し、間隙は連結集合体の外側に開口して配置されている。連結集合体上に担持されたナノ粒子は複数のナノ結晶片とは異なる元素を有する。また、連結集合体に担持されるナノ粒子の量を適切に制御するため、複数のナノ結晶片の視野面積に対するナノ粒子の視野面積の割合は2%以上50%以下である。
次に、本発明に係るナノ結晶複合体の製造方法について説明する。本発明の実施形態であるナノ結晶複合体の製造方法は、混合工程S1と、温度・圧力印加工程S2とを有する。
混合工程は、第一種金属酸化物の原料となる、貴金属、遷移金属またはそれらの合金を含む化合物の水和物、特に金属ハロゲン化物の水和物と、第二種金属酸化物の原料となる、Ceを含む化合物の水和物、特にCeハロゲン化物の水和物と、第一種金属酸化物の前駆体である金属錯体の配位子を構成する炭酸ジアミド骨格を有する有機化合物とを、水溶液(水)に溶かす工程である。金属ハロゲン化物の水和物として、例えば塩化銅(II)二水和物、Ceハロゲン化物の水和物として、例えば塩化セリウム(III)七水和物、炭酸ジアミド骨格を有する有機化合物として、例えば尿素が挙げられる。尚、酸化セリウムと酸化ジルコニウムとの混合体を作製する場合、第二種金属酸化物の原料として、塩化セリウム(III)七水和物とオキシ塩化ジルコニウム八水和物が挙げられる。
水熱合成工程は、得られた混合溶液に所定の熱・圧力を加えて、所定時間、放置する工程である。混用溶液は、100℃以上300℃以下で加熱することが好ましい。加熱温度が100℃未満では、尿素と金属ハロゲン化物との反応を完了させることができず、300℃超では、発生する高蒸気圧に反応容器が耐えられない。加熱時間は、10時間以上であることが好ましい。加熱時間が10時間未満では、未反応の材料が残留する場合がある。所定の圧力は、100℃における水の蒸気圧(1気圧)以上の圧力であることが好ましい。所定の熱・圧力を加えるため、例えば、耐圧容器を用いて加熱・加圧する方法が挙げられる。
室温で150mlのエチレングリコールと150mlの水とを混合し、1時間攪拌して水溶液を作製した。次いで、表1に示す所定の添加量の塩化セリウム(III)七水和物、塩化銅(II)二水和物、尿素を上記水溶液に添加した。得られた溶液を内容積500mlの耐圧容器に注入し、空気雰囲気中で該容器を密閉した。耐圧容器を恒温槽に設置し、180℃で24時間加熱保持後、室温まで冷却した。室温で1日保持した後、沈殿物を含む溶液を容器から回収した。溶液中の沈殿物をメタノールおよび純水で洗浄した後、真空環境下で70℃10時間乾燥させ、ナノ結晶複合体を作製した。
上記のようにして得られた実施例および比較例のナノ結晶複合体を用いて、下記に示す測定及び特性評価を行った。測定及び各特性の評価条件は下記の通りである。結果を表1に示す。
各実施例、比較例で得られたナノ結晶複合体について、EDS(エネルギー分散型X線分光器:株式会社日立ハイテクノロジーズ製「SU−8020」)により、第一種金属酸化物である酸化銅(CuO)と第二種金属酸化物である酸化セリウムナノ粒子(CeO2ナノ粒子)の元素マッピングを行い、CuOの視野面積に対するCeO2ナノ粒子の視野面積の割合(視野面積比率)を測定した。具体的には、観察倍率を20,000倍に設定し、3μm×6μmを1視野としてEDSにて検出された元素ピーク情報からセリウム(Ce)元素と銅(Cu)元素と酸素(O)元素のそれぞれの元素分布を色分けする。次いで、2次元画像元素マッピングを行い、Ce元素とCu元素に相当する面積(視野面積)を算出する。算出したCe元素の面積をCu元素の面積で除して、第一種金属酸化物の視野面積に対する第二種金属酸化物の視野面積の割合とする。以上の操作を無作為に10μm以上離れた視野で合計10視野のマッピングを行い、得られた視野面積の割合の平均値を求め、これを視野面積比率とした。
触媒性能の評価は、ガス供給ライン、反応管およびガスサンプリング部よりなる装置を用いて行った。具体的には以下の通りである。
ナノ結晶の組織観察は、走査型電子顕微鏡(SEM:株式会社日立ハイテクノロジーズ製「SU−8020」)を用いて行った。図2(a)は、実施例2における1回目の600℃触媒評価後のナノ結晶複合体を、倍率4000倍で観察した際のSEM画像であり、図2(b)は、70000倍で観察した際のSEM画像である。
X線回折装置(「D8 DISCOVER」、ブルカー・エイエックスエス株式会社(現ブルカージャパン株式会社)製)による構造解析を行なった。X線結晶構造解析で、触媒反応後の各実施例及び比較例のナノ結晶複合体の組成の同定を行い、酸化銅の結晶構造が維持できているかを確認した。酸化銅の結晶構造が維持できている場合、CuOが存在しているとして「〇」とし、酸化銅の結晶構造が維持できていない場合、CuOの分解が生じているとして「×」と評価した。
20 連結集合体
21 ナノ結晶片
22 主表面
23 端面
30 ナノ粒子
G 間隙
Claims (7)
- 主表面および端面をもつ複数のナノ結晶片が相互に連結された連結集合体と、前記連結集合体に担持されたナノ粒子と、を備え、
前記複数のナノ結晶片のそれぞれが薄片状であり、
前記複数のナノ結晶片が前記主表面間に間隙を有し、
前記間隙が前記連結集合体の外側に開口して配置され、
前記ナノ粒子が前記複数のナノ結晶片とは異なる金属元素を有し、
前記複数のナノ結晶片の視野面積に対する前記ナノ粒子の視野面積の割合が2%以上50%以下であることを特徴とする、ナノ結晶複合体。 - 前記ナノ粒子の粒径が5nm以上100nm以下であり、かつ、
前記ナノ粒子が前記主表面に配置されている、請求項1に記載のナノ結晶複合体。 - 前記複数のナノ結晶片が第一種金属酸化物であり、かつ、
前記ナノ粒子が前記第一種金属酸化物とは異なる第二種金属酸化物である、請求項1又は2に記載のナノ結晶複合体。 - 前記第一種金属酸化物が酸化銅である、請求項3に記載のナノ結晶複合体。
- 前記第二種金属酸化物が酸化セリウムナノ粒子又は酸化セリウムと酸化ジルコニウムとの混合体のナノ粒子である、請求項3又は4に記載のナノ結晶複合体。
- 酸化還元触媒反応に使用するための請求項1乃至5のいずれか1項に記載のナノ結晶複合体。
- 排気ガス浄化用触媒として使用するための請求項1乃至5のいずれか1項に記載のナノ結晶複合体。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019019657 | 2019-02-06 | ||
JP2019019657 | 2019-02-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2020127936A true JP2020127936A (ja) | 2020-08-27 |
Family
ID=71947949
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020014377A Pending JP2020127936A (ja) | 2019-02-06 | 2020-01-31 | ナノ結晶複合体 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20210245141A1 (ja) |
EP (1) | EP3922351A4 (ja) |
JP (1) | JP2020127936A (ja) |
CN (1) | CN112512686A (ja) |
WO (1) | WO2020162336A1 (ja) |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5892465B2 (ja) * | 2011-01-24 | 2016-03-23 | 日産自動車株式会社 | 排気ガス浄化システム |
CN102407123B (zh) * | 2011-09-30 | 2013-08-14 | 内蒙古大学 | 用于CO优先氧化的CuO负载CeO2催化剂 |
CN103055859A (zh) * | 2011-10-21 | 2013-04-24 | 中国科学院合肥物质科学研究院 | 氧化锌-银复合球及其制备方法 |
CN102489303B (zh) * | 2011-11-14 | 2013-04-17 | 青岛科技大学 | 一种铈掺杂NiO分级结构微球的制备方法 |
JP6099238B2 (ja) * | 2012-05-21 | 2017-03-22 | 国立研究開発法人物質・材料研究機構 | ナノ単結晶板材集積触媒 |
JP5816648B2 (ja) * | 2013-04-18 | 2015-11-18 | 三井金属鉱業株式会社 | 排気ガス浄化用触媒組成物及び排気ガス浄化用触媒 |
JP5708767B1 (ja) * | 2013-11-22 | 2015-04-30 | トヨタ自動車株式会社 | 排ガス浄化用触媒及びその製造方法 |
JP6466676B2 (ja) * | 2014-09-18 | 2019-02-06 | 愛媛県 | 可視光応答型光触媒複合体、及び可視光応答型光触媒複合体の製造方法 |
US10512897B2 (en) * | 2015-02-15 | 2019-12-24 | Tianjin University | Micron-scale cerium oxide particle having multi-core single-shell structure and preparation method therefor |
EP3323507B1 (en) * | 2015-07-15 | 2021-04-14 | Furukawa Electric Co. Ltd. | Catalyst comprising an integrated base material and a nanocrystalline metal oxide composite, production method therefor, and catalyst component |
CN109562954B (zh) * | 2017-03-07 | 2022-12-06 | 古河电气工业株式会社 | 薄膜状纳米晶体复合体 |
CN108996477B (zh) * | 2018-07-26 | 2022-02-22 | 四川理工学院 | 一种基于Stober法合成金属氧化物微球的方法 |
-
2020
- 2020-01-31 CN CN202080004110.9A patent/CN112512686A/zh active Pending
- 2020-01-31 WO PCT/JP2020/003581 patent/WO2020162336A1/ja unknown
- 2020-01-31 JP JP2020014377A patent/JP2020127936A/ja active Pending
- 2020-01-31 EP EP20752012.3A patent/EP3922351A4/en active Pending
-
2021
- 2021-04-29 US US17/244,792 patent/US20210245141A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP3922351A4 (en) | 2022-10-12 |
WO2020162336A1 (ja) | 2020-08-13 |
US20210245141A1 (en) | 2021-08-12 |
CN112512686A (zh) | 2021-03-16 |
EP3922351A1 (en) | 2021-12-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2021020377A1 (ja) | 合金ナノ粒子、合金ナノ粒子の集合体、触媒および合金ナノ粒子の製造方法 | |
Muñoz-Fernandez et al. | Solvothermal synthesis of Ag/ZnO and Pt/ZnO nanocomposites and comparison of their photocatalytic behaviors on dyes degradation | |
Kim et al. | Star-shaped Pd@ Pt core–shell catalysts supported on reduced graphene oxide with superior electrocatalytic performance | |
Zhou et al. | Catalysis based on nanocrystals with well‐defined facets | |
JP4035654B2 (ja) | 触媒粒子およびその製造方法 | |
JP6757726B2 (ja) | 基材一体型ナノ結晶金属酸化物複合体含有触媒およびその製造方法ならびに触媒部品 | |
US20050065026A1 (en) | Precious metal - metal oxide composite cluster | |
JP6348352B2 (ja) | 酸素吸蔵材料の製造方法 | |
JP2005185956A (ja) | 触媒粉末、排ガス浄化触媒、及び触媒粉末の製造方法 | |
Nguyen et al. | New experimental evidences of Pt–Pd bimetallic nanoparticles with core–shell configuration and highly fine-ordered nanostructures by high-resolution electron transmission microscopy | |
US11801501B2 (en) | Composite body having nanoparticles uniformly dispersed in nano-sized pores in support, and method for producing same | |
Geng et al. | The unusual nanostructure of nickel–boron catalyst | |
Du et al. | Homogeneous coating of Au and SnO 2 nanocrystals on carbon nanotubes via layer-by-layer assembly: a new ternary hybrid for a room-temperature CO gas sensor | |
JP6734275B2 (ja) | 水素貯蔵・供給用ナノ結晶複合体触媒および水素貯蔵・供給用ナノ結晶複合体触媒混合物並びに水素の供給方法 | |
US11958756B2 (en) | Thin-film-like composite of nanocrystal | |
WO2020162336A1 (ja) | ナノ結晶複合体 | |
Xu et al. | One-pot synthesis of lotus-shaped Pd–Cu hierarchical superstructure crystals for formic acid oxidation | |
JP4296430B2 (ja) | 水性ガスシフト反応用の触媒及びその製造方法 | |
WO2022009870A1 (ja) | 合金、合金ナノ粒子の集合体および触媒 | |
WO2022009871A1 (ja) | 合金、合金ナノ粒子の集合体および触媒 | |
Es-Souni | Supported binary and ternary nanoalloy nanoparticle catalysts-A green processing approach using the leidenfrost layer as nanoreactor | |
Kobayashi et al. | Intermetallic YIr 2 nanoparticles with negatively charged Ir active sites for catalytic hydrogenation of cyclohexanone to cyclohexanol | |
Wang et al. | Fabrication of high-performance CeO 2–MnO x/TiO 2/Ti monolithic catalysts for low-temperature and stable CO oxidation | |
JP7269173B2 (ja) | 結晶配向制御複合体 | |
JP2003286509A (ja) | 複合金属粒子の改質方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD07 | Notification of extinguishment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7427 Effective date: 20210816 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221125 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240104 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240229 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240507 |