JP4784727B2 - Porous composite carrying ultrafine metal particles - Google Patents
Porous composite carrying ultrafine metal particles Download PDFInfo
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- JP4784727B2 JP4784727B2 JP2005067615A JP2005067615A JP4784727B2 JP 4784727 B2 JP4784727 B2 JP 4784727B2 JP 2005067615 A JP2005067615 A JP 2005067615A JP 2005067615 A JP2005067615 A JP 2005067615A JP 4784727 B2 JP4784727 B2 JP 4784727B2
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- metal
- ultrafine
- particles
- porous composite
- carrier
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- 239000002131 composite material Substances 0.000 title claims description 74
- 239000002923 metal particle Substances 0.000 title claims description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 114
- 239000011882 ultra-fine particle Substances 0.000 claims description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 74
- 239000003054 catalyst Substances 0.000 claims description 71
- 239000002245 particle Substances 0.000 claims description 67
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 26
- 230000001681 protective effect Effects 0.000 claims description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- 230000010718 Oxidation Activity Effects 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 229910001111 Fine metal Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 103
- 239000010931 gold Substances 0.000 description 58
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 57
- 229910052737 gold Inorganic materials 0.000 description 56
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 239000011240 wet gel Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 16
- 229910002028 silica xerogel Inorganic materials 0.000 description 16
- 239000000499 gel Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
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- 150000003573 thiols Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000004964 aerogel Substances 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004965 Silica aerogel Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 238000000352 supercritical drying Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- -1 silica Chemical class 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- FVJFRFUSHCIRKP-UHFFFAOYSA-N disodium;hydrogen borate Chemical compound [Na+].[Na+].OB([O-])[O-] FVJFRFUSHCIRKP-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
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- 230000002829 reductive effect Effects 0.000 description 2
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- 230000001954 sterilising effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 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
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Description
本発明は、常温付近あるいは常温以下の低温で、有害物質の酸化分解などに用いられる金属超微粒子担持触媒に関するものであり、更に詳しくは、粒子径がナノスケールに制御された金属超微粒子を金属酸化物を含有する担体に安定に担持させた多孔質複合体、その活性多孔質複合体からなる高い酸化活性を有する触媒、その製造方法及びその用途に関するものである。本発明では、金属超微粒子の粒子径を標準偏差が２ｎｍ以下という狭い粒径分布範囲に制御したナノスケールの金属超微粒子を安定に担持した複合体を製造することができるため、本発明は、従来材と比べて、触媒効率を著しく向上させた触媒材を提供することを可能とし、また、クラスター科学の進展に伴って、画期的、特異的な性質を導き出すことを可能とするものである。 The present invention relates to an ultrafine metal particle-supported catalyst used for oxidative decomposition of toxic substances at a temperature near or below room temperature. More specifically, the present invention relates to ultrafine metal particles whose particle diameter is controlled to nanoscale. The present invention relates to a porous composite stably supported on a support containing an oxide, a catalyst having a high oxidation activity comprising the active porous composite, a method for producing the same, and a use thereof. In the present invention, a composite that stably supports nanoscale metal ultrafine particles in which the particle diameter of the metal ultrafine particles is controlled in a narrow particle size distribution range with a standard deviation of 2 nm or less can be produced. Compared to conventional materials, it is possible to provide catalyst materials with significantly improved catalyst efficiency, and it is possible to derive innovative and specific properties with the progress of cluster science. is there.
粒径約１００ｎｍ以下の金超微粒子は、通常の粗大粒子とは異なった特異な物理的、化学的性質を示すことが知られている（非特許文献１）。しかしながら、超微粒子は、表面エネルギーが大きく、非常に凝固しやすいために、取扱いが困難である。特に、金は、Ｐｔ、Ｐｄ等の他の貴金属に比べて、融点が低く（金：１０６３℃、白金：１７６９℃、パラジウム：１５５０℃）、かつ金属同志の結合が強いために、超微粒子が凝集しやすく、超微粒子としての特徴を充分に引き出すことが困難であった。 It is known that ultrafine gold particles having a particle size of about 100 nm or less exhibit unique physical and chemical properties different from ordinary coarse particles (Non-patent Document 1). However, ultrafine particles are difficult to handle because they have a large surface energy and are very easy to solidify. In particular, gold has a lower melting point than other noble metals such as Pt and Pd (gold: 1063 ° C., platinum: 1769 ° C., palladium: 1550 ° C.) and strong bonding between metals, so that ultrafine particles It was easy to agglomerate and it was difficult to fully extract the characteristics as ultrafine particles.
従来、金超微粒子を金属酸化物担体上に担持、固定化する方法としては、１）共沈法（特許文献１）、２）均一析出沈澱法（特許文献２）、３）滴下中和沈澱法（特許文献３）、４）還元剤添加法（特許文献３）、５）ｐＨ制御中和沈澱法（特許文献３）、６）カルボン酸金属塩添加法（特許文献４）、７）析出沈澱法（特許文献５）、８）コロイド混合法（非特許文献２）、９）気相グラフティング法（特許文献６）、及び１０）液相グラフティング法（非特許文献３）等が知られている。これらの方法において、出発物質が金化合物では、塩化金酸等の金の水溶性化合物が使用され、金属酸化物原料としては、各種金属の硝酸塩、硫酸塩、酢酸塩、塩化物などが使用される。また、上記した共沈法等により、沈澱等を析出させた後、乾燥、焼成する必要がある。（特許文献７） Conventionally, methods for supporting and immobilizing gold ultrafine particles on a metal oxide support include 1) coprecipitation method (Patent Document 1), 2) uniform precipitation method (Patent Document 2), and 3) dropping neutralization precipitation. (Patent Document 3), 4) Reducing agent addition method (Patent Document 3), 5) pH controlled neutralization precipitation method (Patent Document 3), 6) Carboxylic acid metal salt addition method (Patent Document 4), 7) Precipitation Known are precipitation methods (Patent Document 5), 8) colloid mixing method (Non-Patent Document 2), 9) gas phase grafting method (Patent Document 6), and 10) liquid-phase grafting method (Non-Patent Document 3). It has been. In these methods, when the starting material is a gold compound, a gold water-soluble compound such as chloroauric acid is used, and various metal nitrates, sulfates, acetates, chlorides, etc. are used as metal oxide raw materials. The In addition, it is necessary to dry and fire after depositing the precipitate by the coprecipitation method described above. (Patent Document 7)
更に、チタンを主成分とする酸化物からなる担体上に、金超微粒子を均一かつ強固に固定化した複合材料の開発がされてきたが、水溶液のｐＨ値と金水溶性塩やその他の添加物の添加方法などの厳密な作製条件が必要である（特許文献８）。触媒複合体として、平均粒子径が２５ｎｍ以下の金粒子が金属酸化物に担持された金ナノ粒子触媒とアルカリ性多孔質体とを含有する一酸化炭素除去用触媒複合体があるが、金属酸化物に金ナノ粒子を担持する方法に上述した公知の方法を採用していることから、得られる金の析出物が不均一で粗大な塊となりやすい問題点を抱えている（特許文献９）。 Furthermore, composite materials have been developed in which gold ultrafine particles are fixed uniformly and firmly on a carrier composed of an oxide containing titanium as a main component. However, the pH value of an aqueous solution, a water-soluble gold salt, and other additions have been developed. Strict production conditions such as a method for adding a product are required (Patent Document 8). As a catalyst composite, there is a catalyst composite for removing carbon monoxide containing a gold nanoparticle catalyst in which gold particles having an average particle diameter of 25 nm or less are supported on a metal oxide and an alkaline porous body. Since the known method described above is adopted as the method for supporting the gold nanoparticles, the obtained gold precipitate has a problem that it tends to be a non-uniform and coarse lump (Patent Document 9).
上述した公知の方法では、金の析出の条件を精密に制御することが不可欠であり、また、金を担持させるために長時間を要するという欠点がある。更に、金の水溶液から金成分を部分的に沈殿析出させるため、金の利用率が低く、製造コストが高くなるという欠点もある。また、得られる金の析出物が不均一で粗大なかたまりとなり易く、金析出物の粒径の制御が困難な問題点を抱えている。 In the known method described above, it is indispensable to precisely control the conditions for gold deposition, and there is a drawback that it takes a long time to support gold. Furthermore, since the gold component is partially precipitated from an aqueous solution of gold, there are also disadvantages that the utilization rate of gold is low and the manufacturing cost is high. In addition, the obtained gold precipitates are likely to be non-uniform and coarse masses, and it is difficult to control the particle size of the gold precipitates.
そこで、表面保護した金属超微粒子をテトラヒドロフランなど弱極性の有機溶媒に溶かした後、この溶液にウェットゲルを浸漬し、金属超微粒子をゲル内に吸収させ、得られた金属超微粒子・ウェットゲル複合体をトルエン等の無極性の有機溶媒に浸漬することにより、ゲル骨格に固着、乾燥、加熱を行うことで、サイズ制御して作製した金属超微粒子の粒子サイズを変化させることなくウェットゲル中に分散させる方法が開発された（特許文献１０、１１）。 Therefore, after dissolving the surface-protected metal ultrafine particles in a weakly polar organic solvent such as tetrahydrofuran, the wet gel is immersed in this solution to absorb the metal ultrafine particles into the gel, and the resulting metal ultrafine particles / wet gel composite is obtained. By immersing the body in a non-polar organic solvent such as toluene, it is fixed to the gel skeleton, dried, and heated, so that the particle size of the ultrafine metal particles produced by controlling the size is not changed in the wet gel. A method of dispersing was developed (Patent Documents 10 and 11).
しかし、この作製法では、化合物の種類や濃度により、金属超微粒子がゲル内部への浸透に長時間を要し、内部まで十分浸透しないため、金属超微粒子が全量担持されず、不均一に分散されたものが多々見られた。また、金属超微粒子・ウェットゲル複合体の粒度を揃える工程で、金属超微粒子の損失が生じる問題を抱えている。更に、この金属超微粒子・ウェットゲル複合体の触媒機能に関しての報告はされていなかった。 However, in this production method, depending on the type and concentration of the compound, the ultrafine metal particles take a long time to penetrate into the gel and do not penetrate sufficiently into the inside of the gel. Many things were seen. In addition, there is a problem that loss of ultrafine metal particles occurs in the process of aligning the particle sizes of the ultrafine metal particle / wet gel composite. Furthermore, there has been no report on the catalytic function of the ultrafine metal particle / wet gel composite.
ホルムアルデヒドの除去法としては、吸着法と酸化法が知られている。吸着法はホルムアルデヒドを活性炭などの高比表面積を有する吸着剤に吸着させて除去する方法であるが、吸着剤の交換や再生を必要とする欠点がある。これに対し、酸化分解法はホルムアルデヒドを二酸化炭素と水に分解し、無害化する方法であり、ホルムアルデヒドを完全に除去できるという利点がある。しかし、従来のホルムアルデヒドを酸化分解して除去できる酸化触媒は、金属酸化物上に貴金属粒子を公知の方法で固定化したものであり、沈殿物の分離と攪拌の操作を４回繰り返す手間がかかる。更に、触媒の粒度を揃える工程で損失が生じるという問題点を抱えている。（特許文献１２）。 As a method for removing formaldehyde, an adsorption method and an oxidation method are known. The adsorption method is a method in which formaldehyde is adsorbed and removed by an adsorbent having a high specific surface area such as activated carbon, but has a drawback that the adsorbent needs to be replaced or regenerated. On the other hand, the oxidative decomposition method is a method in which formaldehyde is decomposed into carbon dioxide and water and rendered harmless, and has an advantage that formaldehyde can be completely removed. However, a conventional oxidation catalyst capable of removing formaldehyde by oxidative decomposition is obtained by immobilizing noble metal particles on a metal oxide by a known method, and it takes time and effort to separate the precipitate and agitation four times. . Furthermore, there is a problem that a loss occurs in the process of making the particle size of the catalyst uniform. (Patent Document 12).
このような状況下にあって、本発明者らは、上記従来技術に鑑みて、シリカ、アルミナ、チタニア、ジルコニアなどの金属酸化物を含有する担体に、金属超微粒子を分散させた状態で固定されてなる多孔質複合体の簡便な製造方法と、常温で高い酸化活性を有する触媒を開発することを目標として鋭意研究を積み重ねた結果、本発明を成すに至った。本発明は、担体が溶媒に溶解した表面保護物質で保護された金属超微粒子を自発的に凝集することなく吸着し、金属超微粒子を損失することなく固定したことを特徴とする多孔質複合体、その製造方法、常温付近あるいは常温以下の低温で高い酸化活性を有する金属超微粒子担持触媒、及びその用途を提供することを目的とするものである。 Under such circumstances, in view of the above prior art, the present inventors fixed the metal ultrafine particles dispersed in a carrier containing a metal oxide such as silica, alumina, titania and zirconia. As a result of intensive research aimed at developing a simple method for producing a porous composite and a catalyst having high oxidation activity at room temperature, the present invention has been achieved. The present invention relates to a porous composite characterized in that a carrier is adsorbed without spontaneously agglomerating metal ultrafine particles protected with a surface protective substance dissolved in a solvent, and the metal ultrafine particles are fixed without loss. It is an object of the present invention to provide a production method thereof, a metal ultrafine particle-supported catalyst having high oxidation activity at a temperature near or below room temperature, and a use thereof.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）金属酸化物を含有する担体に、表面保護物質で保護したナノスケールの金属超微粒子を分散させた状態で固定してなる多孔質複合体であって、
上記担体が、シリカ、アルミナ、チタニア、又はジルコニアの多孔質体の表面に金属酸化物が被覆された構造を有する金属酸化物被覆多孔体からなる表面積２００ｍ ２ ／ｇ以上の乾燥担体から構成され、上記金属超微粒子が、貴金属、及び遷移金属から選択される１種又は複数種であり、上記金属超微粒子が予め作製した金属超微粒子の粒子サイズそのままに上記ナノスケールの金属超微粒子の粒子径の標準偏差が２ｎｍ又はそれ以下の値に制御されて担持されていることを特徴とする多孔質複合体。
（２）担体が、比表面積が２００ｍ２／ｇ以上の乾燥エアロゲル又はキセロゲルである前記（１）に記載の多孔質複合体。
（３）ナノスケールの金属超微粒子が、粒子径が大きくても２０ｎｍの超微粒子である前記（１）に記載の多孔質複合体。
（４）前記（１）から（３）のいずれかに記載の多孔質複合体を構成する金属超微粒子の表面保護物質を除去した活性多孔質複合体からなることを特徴とする酸化活性を有する触媒。
（５）表面保護物質で保護したナノスケールの金属超微粒子を溶液中で熱処理して粒子径を制御し、これを溶媒中に分散させ、担体と接触させることにより、該担体に、上記金属超微粒子を分散させた状態で固定して多孔質複合体を製造する方法であって、
上記担体が、シリカ、アルミナ、チタニア、又はジルコニアの多孔質体の表面に金属酸化物が被覆された構造を有する金属酸化物被覆多孔体からなる表面積２００ｍ ２ ／ｇ以上の乾燥担体から構成され、上記金属超微粒子が、貴金属、及び遷移金属から選択される１種又は複数種であり、予め所定の形状に揃えた乾燥担体を用いて担持操作を行うことで該乾燥担体に金属超微粒子をその担持量を制御して担持させることにより上記ナノスケールの金属超微粒子の粒子径の標準偏差を２ｎｍ又はそれ以下の値に制御することを特徴とする多孔質複合体の製造方法。
（６）担体が、比表面積が２００ｍ２／ｇ以上の乾燥エアロゲル又はキセロゲルである前記（５）に記載の多孔質複合体の製造方法。
（７）前記（５）に記載の方法で得られる多孔質複合体を熱処理して金属超微粒子の表面保護物質を除去することを特徴とする活性多孔質複合体からなる酸化活性を有する触媒の製造方法。
（８）金属超微粒子として、金属イオンを表面保護物質の存在下で還元し、表面保護物質で保護した金属超微粒子を用いる前記（５）に記載の多孔質複合体の製造方法。
（９）表面保護物質で保護した金属超微粒子を溶液中で熱処理することにより、金属超微粒子の粒子径を制御する前記（５）に記載の多孔質複合体の製造方法。
（１０）有機溶媒中に分散させた金属超微粒子を担体と接触させ、吸着させることで、担体に金属超微粒子を凝集することなく固定する前記（５）に記載の多孔質複合体の製造方法。
（１１）前記（４）に記載の触媒の粉末を含むことを特徴とする酸化作用を有する部材。
（１２）前記（４）に記載の触媒の成形体を含むことを特徴とする酸化作用を有する部材。
（１３）部材が、ＶＯＣ浄化手段である前記（１１）又は（１２）に記載の部材。
（１４）部材が、一酸化炭素除去フィルターである前記（１１）又は（１２）に記載の部材。
（１５）部材が、空気洗浄機又は空気洗浄フィルターである前記（１１）又は（１２）に記載の部材。
The present invention for solving the above-described problems comprises the following technical means.
(1) A porous composite formed by fixing nanoscale metal ultrafine particles protected with a surface protective substance on a carrier containing a metal oxide in a dispersed state,
The carrier is composed of a dry carrier having a surface area of 200 m 2 / g or more comprising a metal oxide-coated porous body having a structure in which a metal oxide is coated on the surface of a porous body of silica, alumina, titania, or zirconia, The ultrafine metal particles are one or more selected from precious metals and transition metals, and the ultrafine metal particles have the same particle size as the ultrafine metal particles prepared in advance . porous composite standard deviation is characterized that you have been carried is controlled to 2nm or less value.
(2) The porous composite according to (1), wherein the carrier is a dry airgel or xerogel having a specific surface area of 200 m 2 / g or more.
(3) The porous composite according to (1), wherein the nanoscale ultrafine metal particles are ultrafine particles of 20 nm even if the particle diameter is large.
(4) It has an oxidation activity characterized by comprising an active porous composite from which the surface protective material of the metal ultrafine particles constituting the porous composite according to any one of (1) to (3) is removed. catalyst.
(5) Nanoscale metal ultrafine particles protected with a surface protective substance are heat-treated in a solution to control the particle size, and this is dispersed in a solvent and brought into contact with the carrier, whereby the above-mentioned metal ultrafine particles are brought into contact with the carrier. A method for producing a porous composite by fixing fine particles in a dispersed state,
The carrier is composed of a dry carrier having a surface area of 200 m 2 / g or more comprising a metal oxide-coated porous body having a structure in which a metal oxide is coated on the surface of a porous body of silica, alumina, titania, or zirconia, The metal ultrafine particles are one or more selected from precious metals and transition metals, and the carrying operation is performed using a dry carrier having a predetermined shape in advance so that the ultrafine metal particles are added to the dry carrier. method for producing a porous composite which is characterized that you control the 2nm or less value the standard deviation of the particle diameter of the nano-scale ultra-fine metal particles by supporting by controlling the carrying amount.
(6) The method for producing a porous composite according to (5), wherein the carrier is a dry airgel or xerogel having a specific surface area of 200 m 2 / g or more.
(7) A catalyst having an oxidation activity comprising an active porous composite, wherein the porous composite obtained by the method described in (5) above is heat-treated to remove the surface protective material of the metal ultrafine particles. Production method.
(8) The method for producing a porous composite according to (5), wherein metal ultrafine particles obtained by reducing metal ions in the presence of a surface protective substance and protecting the metal ions with the surface protective substance are used as the metal ultrafine particles.
(9) The method for producing a porous composite according to (5), wherein the particle diameter of the metal ultrafine particles is controlled by heat-treating the metal ultrafine particles protected with the surface protective substance in a solution.
(10) The method for producing a porous composite according to the above (5), wherein the metal ultrafine particles dispersed in the organic solvent are brought into contact with the carrier and adsorbed to fix the metal ultrafine particles on the carrier without aggregation. .
(11) A member having an oxidizing action, comprising the catalyst powder according to (4).
(12) A member having an oxidizing action, comprising a molded product of the catalyst according to (4).
(13) The member according to (11) or (12), wherein the member is a VOC purification unit.
(14) The member according to (11) or (12), wherein the member is a carbon monoxide removal filter.
(15) The member according to (11) or (12), wherein the member is an air cleaning machine or an air cleaning filter.
次に、本発明について更に詳細に説明する。
本発明は、シリカ、アルミナ、チタニア、ジルコニアなどの金属酸化物を含有する担体に、金属超微粒子を分散させた状態で固定して多孔質複合体としたこと、また、必要により、金属超微粒子の表面保護物質を除去して活性多孔質複合体としたことを特徴とするものである。本発明は、チオールに代表される表面保護物質を表面に吸着させることにより安定化させた金属超微粒子を含む溶媒溶液中に、多孔質材料、好ましくはエアロゲルあるいはキセロゲルを上記溶媒に置換したものに浸すことを一つの構成要素としており、これにより、安定化された金属超微粒子が凝集等の構造変化を起こすことなく、自発的にエアロゲル及びキセロゲルの内部表面に吸着される。その後、溶媒を除去し、乾燥することで多孔質複合体が得られる。また、導入する金属超微粒子の濃度は、浸す溶液中の金属超微粒子の濃度を変化させることにより制御することができる。また、本発明は、金属超微粒子が凝集することなく溶媒溶液として最初に導入されたものと同じ大きさのまま、多孔質材料中に均一に担持された多孔質複合体が得られる。また、必要に応じ、予め粒度制御を行った担体を用いることで、粒度制御された複合体を作製することができる。
Next, the present invention will be described in more detail.
In the present invention, a porous composite is obtained by fixing a metal oxide such as silica, alumina, titania, zirconia or the like in a state where the metal ultrafine particles are dispersed, and if necessary, the metal ultrafine particles. The surface protective substance is removed to obtain an active porous composite. In the present invention, a porous material, preferably an airgel or xerogel is substituted with the above solvent in a solvent solution containing ultrafine metal particles stabilized by adsorbing a surface protective substance typified by thiol on the surface. The soaking is one component, whereby the stabilized ultrafine metal particles are spontaneously adsorbed on the inner surfaces of the airgel and xerogel without causing structural changes such as aggregation. Thereafter, the solvent is removed and the porous composite is obtained by drying. Further, the concentration of the ultrafine metal particles to be introduced can be controlled by changing the concentration of the ultrafine metal particles in the solution to be immersed. The present invention also provides a porous composite that is uniformly supported in a porous material while maintaining the same size as that initially introduced as a solvent solution without aggregation of ultrafine metal particles. Moreover, the composite body by which the particle size control was carried out can be produced by using the support | carrier which performed particle size control beforehand as needed.
本発明において、上記金属超微粒子としては、好ましくは、例えば、金、銀、パラジウムなどの貴金属、鉄、コバルトなどの遷移金属が使用される。また、上記チオールに代表される表面保護物質としては、例えば、ドデカンチオール、ベンゼンチオール等のチオール類、トリフェニルホスフィン等のリン化合物などの金属超微粒子を溶媒溶液中で安定化させる適宜の試薬が用いられる。これらは、溶媒溶液中で金属が凝集せずに安定に存在できる組み合わせであればよく、金属超微粒子及びそれを安定化させる試薬ともに上述のものに限定されるものではない。本発明において、上記チオールに代表される表面保護物質とは、このように、金属超微粒子を溶媒溶液中で安定化させる適宜の試薬を意味するものとして定義される。また、上述の作製方法による金属超微粒子の粒径は、１〜２０ｎｍ程度のものが一般的ではあるが、特に、この粒径域に限定するものではない。金超微粒子の大きさは特に限定されるものではないが、粒子径が１０ｎｍ以下である、いわゆる超微粒子がより好適である。 In the present invention, as the ultrafine metal particles, for example, noble metals such as gold, silver and palladium, and transition metals such as iron and cobalt are preferably used. Examples of the surface protective substance typified by the thiol include an appropriate reagent for stabilizing metal ultrafine particles such as thiols such as dodecanethiol and benzenethiol and phosphorus compounds such as triphenylphosphine in a solvent solution. Used. These may be any combination that allows metal to stably exist without aggregating in the solvent solution, and both the metal ultrafine particles and the reagent that stabilizes them are not limited to those described above. In the present invention, the surface protective substance typified by the thiol is defined as meaning an appropriate reagent for stabilizing the metal ultrafine particles in the solvent solution. Moreover, although the particle diameter of the metal ultrafine particles by the above-mentioned production method is generally about 1 to 20 nm, it is not particularly limited to this particle size range. The size of the gold ultrafine particles is not particularly limited, but so-called ultrafine particles having a particle diameter of 10 nm or less are more preferable.
本発明で用いられる多孔質材料としては、好ましくは比表面積が２００ｍ２／ｇ以上あるエアロゲルあるいはキセロゲルが例示される。これらには、シリカ、チタニア、ジルコニア、アルミナ等の金属酸化物の単体あるいは複合体を用いることができるが、担持される金属超微粒子の触媒性能を十分に引き出すために、ある特定の化学種の担体表面上に金属超微粒子を担持することが必要である。その特定の化学種単体などの多孔質体を用いて、本発明の方法で、金属超微粒子を担持した場合、多孔質体の構造変化などの問題が起こるときには、シリカなどの骨格の表面に必要とする金属酸化物を被覆したエアロゲル、キセロゲルなどを用いることができる。 The porous material used in the present invention is preferably an airgel or xerogel having a specific surface area of 200 m 2 / g or more. For these, a simple substance or a composite of metal oxides such as silica, titania, zirconia, and alumina can be used. However, in order to sufficiently bring out the catalytic performance of the supported ultrafine metal particles, a specific chemical species is used. It is necessary to carry metal ultrafine particles on the surface of the carrier. When a porous material such as a specific chemical species is used and metal ultrafine particles are supported by the method of the present invention, it is necessary on the surface of the skeleton such as silica when problems such as structural changes of the porous material occur. An airgel or xerogel coated with a metal oxide can be used.
具体的には、例えば、金超微粒子を常温酸化触媒として用いる場合、担体表面としては、チタニアなどが望ましいが、チタニア担体のエアロゲル等を用いると、後に述べる、保護分子除去のための熱処理時にチタニアの相変化が起こり、多孔質体の構造が大きく変化するとともに、それに伴い金の凝集が起こってしまう。シリカ表面にチタニアを被覆したエアロゲル等を用いることにより、熱処理での相変化が抑えられ、金の凝集が起こらずに、高い性能を示す材料が得られる。これらのエアロゲルやキセロゲルは、ウェットゲルの作製と、その超臨界乾燥あるいは自然乾燥により作製される。 Specifically, for example, when gold ultrafine particles are used as a room temperature oxidation catalyst, titania or the like is desirable as the support surface. However, when a titania support aerogel or the like is used, titania is used during heat treatment for protecting molecule removal described later. As a result of this phase change, the structure of the porous body changes greatly, and gold agglomerates accordingly. By using an airgel or the like whose surface is coated with titania on the silica surface, a phase change due to heat treatment can be suppressed, and a material exhibiting high performance can be obtained without causing aggregation of gold. These aerogels and xerogels are produced by production of wet gel and its supercritical drying or natural drying.
ウェットゲルの作製は、通常、例えば、シリカウエットゲルであれば、ケイ酸メチルやケイ酸エチル等の金属アルコキシドの加水分解とゲル化により作製されるが、以下の溶媒置換などに耐える程度のウェットゲルが得られるならば、それらの物質及び作製法ともにこれらに限定されるものではない。また、エアロゲル及びキセロゲルを作製する場合、例えば、金属アルコキシドをエタノールなどのアルコールで希釈して、かつ、加水分解を行わせることにより、各種の酸化物濃度のウェットゲルを得ることができ、当該ウェットゲル及びその乾燥法により各種濃度の多孔質材料を得ることができる。 Preparation of wet gel is usually made by hydrolysis and gelation of metal alkoxides such as methyl silicate and ethyl silicate, for example, if it is silica wet gel, but wet enough to withstand the following solvent substitution. As long as a gel can be obtained, the materials and the production method are not limited to these. Further, when producing airgel and xerogel, for example, by diluting a metal alkoxide with an alcohol such as ethanol and performing hydrolysis, wet gels having various oxide concentrations can be obtained. Various concentrations of porous material can be obtained by gel and its drying method.
ウェットゲルを、例えば、チタンテトライソプロポキシドのトルエン溶液等に浸漬して、１日程度静置し、未反応のアルコキシドを液相を純トルエンに置換することで除去してから、乾燥することで、チタニア被覆シリカウエットゲルが得られる。ウェットゲルは、自然乾燥によりキセロゲル、超臨界乾燥によりエアロゲルとされる。自然乾燥は、通常は、室温、大気中で数日放置という方法で行われるが、溶媒の種類、乾燥時の収縮防止の観点から、若干の加熱、あるいは減圧下の乾燥等、各種の条件設定を行うことが可能であり、乾燥して多孔質体が得られるならば、上述の方法に限られるものではない。 The wet gel is immersed in, for example, a toluene solution of titanium tetraisopropoxide and left to stand for about 1 day, and the unreacted alkoxide is removed by replacing the liquid phase with pure toluene, followed by drying. Thus, a titania-coated silica wet gel is obtained. The wet gel is made into a xerogel by natural drying and an airgel by supercritical drying. Natural drying is usually performed by leaving it to stand at room temperature in the atmosphere for several days, but various conditions such as slight heating or drying under reduced pressure are used from the viewpoint of the type of solvent and prevention of shrinkage during drying. As long as the porous body can be obtained by drying, the method is not limited to the above.
また、超臨界乾燥を用いる場合は、乾燥に必要な温度が低くてよいように、好適には、専ら二酸化炭素媒体の超臨界乾燥が用いられる。ウェットゲルをオートクレーブ中に入れて、ウェットゲルの液相溶媒でオートクレーブを満たし、加圧下で液相を液化二酸化炭素に置換した後、オートクレーブ内を二酸化炭素の臨界条件以上、例えば、５０℃、１０ＭＰａとして二酸化炭素を超臨界流体とした後、温度を維持しつつ二酸化炭素を除去して多孔質材料を得る。この方法により、極めて低密度な多孔質体が得られる。なお、超臨界媒体は、二酸化炭素に限られるものではない。このようにして作製した、エアロゲル、キセロゲルは、そのまま金属超微粒子吸着操作が進んでもよく、また、表面残留有機基などの除去のため１０００℃以下で１〜５時間熱処理を行ってもよい。最も好ましくは、表面残留有機基の脱離する温度以上で、２〜４時間熱処理を行う。 When supercritical drying is used, preferably, supercritical drying of a carbon dioxide medium is preferably used so that the temperature required for drying may be low. The wet gel is put in an autoclave, the autoclave is filled with the liquid solvent of the wet gel, and the liquid phase is replaced with liquefied carbon dioxide under pressure. As a supercritical fluid, carbon dioxide is removed while maintaining the temperature to obtain a porous material. By this method, an extremely low density porous body can be obtained. Note that the supercritical medium is not limited to carbon dioxide. The aerogel and xerogel produced in this manner may be subjected to the ultrafine metal particle adsorption operation as they are, and may be heat-treated at 1000 ° C. or lower for 1 to 5 hours for removing surface residual organic groups. Most preferably, the heat treatment is performed at a temperature equal to or higher than the temperature at which the surface residual organic groups are eliminated.
本発明で用いられる多孔質複合体は、有機溶媒を媒体として金属超微粒子が凝集することなく担体へ固定された状態を特徴とするものである。具体的には、例えば、金属超微粒子が金の場合、担体には粒径制御されたチタニア被覆シリカエアロゲル又はチタニア被覆シリカキセロゲルを用い、溶媒にトルエン又はテトラヒドロフランを用いて、金を溶解し、そこへ担体を投入し、溶媒中で金が全て担体へ固定された状態とすることで多孔質複合体となる。 The porous composite used in the present invention is characterized by a state in which ultrafine metal particles are fixed to a carrier without aggregation using an organic solvent as a medium. Specifically, for example, when the ultrafine metal particles are gold, a titania-coated silica aerogel or titania-coated silica xerogel having a controlled particle size is used as a support, and toluene or tetrahydrofuran is used as a solvent to dissolve gold. The support is put into the substrate, and all the gold is fixed to the support in a solvent to form a porous composite.
更に、上記多孔質複合体の製造方法において、使用する有機溶媒は、金属超微粒子を溶解できるものであれば特に限定されるものではない。具体的には、例えば、アルコール類、ケトン類、エーテル類、エステル類、及び炭化水素類が挙げられる。アルコール類としては、具体的には、例えば、メチルアルコール、エチルアルコール、イソプロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、オクチルアルコール、エチレングリコール等が挙げられる。ケトン類としては、具体的には、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。エーテル類としては、具体的には、例えば、テトラヒドロフラン、ジイソブチルエーテル等が挙げられる。エステル類としては、具体的には、例えば、酢酸エチル、酢酸ブチル、プロピオン酸メチル等が挙げられる。炭化水素類としては、具体的には、例えば、ヘキサン、トルエン、キシレン等が挙げられる。 Furthermore, in the method for producing a porous composite, the organic solvent to be used is not particularly limited as long as it can dissolve the metal ultrafine particles. Specific examples include alcohols, ketones, ethers, esters, and hydrocarbons. Specific examples of alcohols include methyl alcohol, ethyl alcohol, isopropyl alcohol, isopropyl alcohol, n-butyl alcohol, octyl alcohol, and ethylene glycol. Specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of ethers include tetrahydrofuran and diisobutyl ether. Specific examples of the esters include ethyl acetate, butyl acetate, and methyl propionate. Specific examples of the hydrocarbons include hexane, toluene, xylene and the like.
上述した多孔質複合体を粉砕及び分級により粒度をそろえ、金属超微粒子を担持する条件は、安定化された金属超微粒子を含むトルエンに代表される有機溶媒溶液中に粒度をそろえたエアロゲル及びキセロゲルを浸し、室温にて０．５〜２４時間攪拌する。この程度で溶液中の金属超微粒子は、エアロゲル及びキセロゲルの内部表面に吸着される。通常、金属超微粒子を含む溶液は着色しており、エアロゲル及びキセロゲルは無色で半透明かほぼ透明であるので、エアロゲル及びキセロゲル側が着色していき、溶液側が無色透明等溶媒本来の色になっていくことから反応の進行がわかる。溶液中の金属超微粒子の濃度、及び溶液量とエアロゲル及びキセロゲル量の比率を変えることにより、最終的に得られる多孔質体中の金属超微粒子の濃度を変化させることができる。 The above-mentioned porous composite has the same particle size by pulverization and classification, and the conditions for supporting the metal ultrafine particles are aerogels and xerogels with uniform particle sizes in an organic solvent solution typified by toluene containing stabilized metal ultrafine particles. And stir at room temperature for 0.5-24 hours. At this level, the ultrafine metal particles in the solution are adsorbed on the inner surfaces of the airgel and xerogel. Usually, the solution containing ultrafine metal particles is colored, and the airgel and xerogel are colorless and translucent or almost transparent, so the aerogel and xerogel side is colored, and the solution side becomes the original color of the solvent such as colorless and transparent. You can see the progress of the reaction. By changing the concentration of the ultrafine metal particles in the solution and the ratio of the solution amount and the amount of the airgel and xerogel, the concentration of the ultrafine metal particles in the porous body finally obtained can be changed.
従来の方法では、金属微粒子の担持量を３ｗｔ％担持するのに３日間以上必要だが、本発明の製造方法を用いると、３０分以内に金属超微粒子を全量担持することができる。更に、金属微粒子の濃度を５倍（１５ｗｔ％）にすると、３日間で金属超微粒子を全量担持することができる。本発明では、金属超微粒子を担持した多孔質複合体を熱処理することにより表面保護物質を除去するが、保護物質の脱離する温度は、示差熱分析や熱重量分析等により見積もることができる。多孔質材料中の金属超微粒子からの保護物質の脱離は、例えば、電気炉中で、その脱離温度より１０℃程度高い温度で１時間程度、熱処理することにより達成される。なお、加熱装置、温度、加熱時間は、保護物質の脱離に十分であればよく、上記のものに限るものではない。 In the conventional method, it takes 3 days or more to support 3 wt% of the fine metal particles. However, when the production method of the present invention is used, all the ultrafine metal particles can be supported within 30 minutes. Furthermore, when the concentration of the metal fine particles is increased to 5 times (15 wt%), the entire amount of metal ultrafine particles can be supported in 3 days. In the present invention, the surface protective substance is removed by heat-treating the porous composite carrying the metal ultrafine particles, but the temperature at which the protective substance is desorbed can be estimated by differential thermal analysis or thermogravimetric analysis. The desorption of the protective substance from the ultrafine metal particles in the porous material is achieved, for example, by heat treatment in an electric furnace at a temperature about 10 ° C. higher than the desorption temperature for about 1 hour. Note that the heating device, temperature, and heating time are not limited to those described above as long as they are sufficient for desorption of the protective substance.
本発明では、上記表面保護物質を除去して、活性多孔質複合体とすることにより、高い酸化活性を有する触媒を作製することができる。本発明の上記活性多孔質複合体からなる触媒では、例えば、金属超微粒子の粒子径を標準偏差が２ｎｍ以下という狭い粒径分布範囲に制御した金属超微粒子を安定に担持させることが可能であり、金属超微粒子の粒子径を制御し、担持量を増加させることで触媒効果を著しく向上させることが可能であり、それにより、本発明は、従来材と比べて、高い酸化活性等を有する高機能の触媒を提供することが実現できる。本発明の触媒は、例えば、常温付近あるいは常温以下の低温で、有害物質の酸化分解に好適に使用することができるものであり、例えば、空気清浄機又は空気浄化フィルター、ＶＯＣ浄化フィルター、一酸化炭素除去フィルター、医療又は食品用の消毒、又は殺菌材料等の部材を構成する活性触媒として有用である。 In the present invention, a catalyst having high oxidation activity can be produced by removing the surface protective substance to obtain an active porous composite. In the catalyst comprising the above active porous composite of the present invention, for example, it is possible to stably support ultrafine metal particles in which the particle size of ultrafine metal particles is controlled to a narrow particle size distribution range with a standard deviation of 2 nm or less. It is possible to remarkably improve the catalytic effect by controlling the particle diameter of the ultrafine metal particles and increasing the supported amount, whereby the present invention has a high oxidation activity and the like compared to conventional materials. Providing a functional catalyst can be realized. The catalyst of the present invention can be suitably used for oxidative decomposition of harmful substances at, for example, near room temperature or at a low temperature of room temperature or less. For example, an air cleaner or an air purification filter, a VOC purification filter, a monoxide It is useful as an active catalyst constituting members such as carbon removal filters, medical or food disinfection, or sterilizing materials.
以上詳述したように、本発明は、多孔質材料に金属超微粒子を担持した多孔質複合体及びその作製方法に係るものであり、本発明によれば、１）予め作製した直径１〜２０ｎｍの金属超微粒子の粒子サイズそのままに、金属超微粒子を担持した多孔質複合体を、その担持量を制御して作製することができる、２）また、多孔質材料に分散して担持されている金属超微粒子を、凝集することなく表面保護物質を除去することができる、３）触媒等への応用において、金属超微粒子を担持した多孔質複合体の金属超微粒子の担持量の増加及び金属超微粒子の粒子径を制御することで、触媒効率を向上させることができる、４）また、数ｎｍサイズの金属超微粒子では量子サイズ効果も期待され、非線形光学材料など量子サイズ効果を用いた材料等への応用が期待される、という格別の効果が奏される。 As described above in detail, the present invention relates to a porous composite in which ultrafine metal particles are supported on a porous material and a method for producing the same. According to the present invention, 1) a diameter of 1 to 20 nm prepared in advance. It is possible to produce a porous composite carrying metal ultrafine particles with the particle size of the metal ultrafine particles as they are, by controlling the carrying amount. 2) In addition, they are dispersed and carried in a porous material. The surface protective substance can be removed without agglomerating the ultrafine metal particles. 3) In application to a catalyst, etc., the amount of ultrafine metal particles supported on the porous composite carrying ultrafine metal particles and the ultrafine metal particles are reduced. By controlling the particle size of the fine particles, the catalyst efficiency can be improved. 4) In addition, a few nanometer-sized metal ultrafine particles are also expected to have a quantum size effect, and materials using the quantum size effect such as nonlinear optical materials, etc. Application is expected, special effect can be attained.
次に、実施例により本発明を具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by the following examples.
（１）金超微粒子の作製
塩化金酸４水和物０．５００ｇ（１．２１４ｍｍｏｌ）に蒸留水１０ｍｌを加えて塩化金酸水溶液とした。これと、トルエン８０ｍｌに臭化テトラオクチルアンモニウム０．７２４ｇ（１．４５７ｍｍｏｌ）を加えたトルエン溶液を混合し、５〜１０分撹拌することにより、塩化金酸イオンをトルエン相に抽出した。トルエン相を分離・抽出し、これにドデカンチオール０．８７１ｍｌ（３．６４２ｍｍｏｌ）を加え、３０分撹拌した。この溶液にホウ酸水素ナトリウム０．５１０ｇ（１３．４９ｍｍｏｌ）に蒸留水５ｍｌを加えたホウ酸水素ナトリウム水溶液を滴下し、１時間撹拌することにより金イオンを還元した。トルエン相を分離・抽出した後、溶液を約１０ｍｌまで濃縮し、エタノール１００ｍｌと混合した。この混合液を−３０℃で保存することにより、金超微粒子を析出させた。生成した金超微粒子は、トルエン−エタノール混合液から再結晶させることにより２回精製した。生成した粒子の金コアの直径は平均２．６ｎｍであった。粒径分布の半値巾は約２ｎｍであった。
(1) Production of ultrafine gold particles 10 ml of distilled water was added to 0.500 g (1.214 mmol) of chloroauric acid tetrahydrate to obtain an aqueous chloroauric acid solution. This and a toluene solution obtained by adding 0.724 g (1.457 mmol) of tetraoctylammonium bromide to 80 ml of toluene were mixed and stirred for 5 to 10 minutes to extract chloroauric acid ions to the toluene phase. The toluene phase was separated and extracted, and 0.871 ml (3.642 mmol) of dodecanethiol was added thereto and stirred for 30 minutes. To this solution, a sodium hydrogen borate aqueous solution in which 5 ml of distilled water was added to 0.510 g (13.49 mmol) of sodium hydrogen borate was dropped, and the mixture was stirred for 1 hour to reduce gold ions. After separating and extracting the toluene phase, the solution was concentrated to about 10 ml and mixed with 100 ml of ethanol. By storing this mixed solution at −30 ° C., ultrafine gold particles were precipitated. The produced gold ultrafine particles were purified twice by recrystallization from a toluene-ethanol mixed solution. The average diameter of the gold core of the produced particles was 2.6 nm. The half width of the particle size distribution was about 2 nm.
（２）シリカウエットゲルの作製
テトラメチルシリケイト１２１．６ｇにメタノール２５６ｇを混合し、撹拌した。その後、撹拌しながら溶液中にアンモニア水（０．００５Ｎ）８６．４ｇを加えた。この時、テトラメチルシリケイトとメタノール、水の比はモル比で１：１０：６であった。１分ほど撹拌した後、混合液を円柱形の型（直径８０ｍｍ、深さ１０ｍｍ）に流し込み、蓋をした。これを約１時間放置し、反応液がゼリー状に固まっていることを確認してから、乾燥するのを防ぐため、ポリ塩化ビニリデンフィルムで密封した。その後、１日放置し、ゲル化を進行させた。その後、型から取り出し、エタノールに浸して１日以上放置した。ゲル中に残存する水やアンモニアを完全に除去するため、その後、エタノールの取替えを２回行った。
(2) Production of silica wet gel 256 g of methanol was mixed with 121.6 g of tetramethyl silicate and stirred. Thereafter, 86.4 g of aqueous ammonia (0.005N) was added to the solution while stirring. At this time, the ratio of tetramethyl silicate to methanol and water was 1: 10: 6 in molar ratio. After stirring for about 1 minute, the mixed solution was poured into a cylindrical mold (diameter 80 mm, depth 10 mm) and covered. This was allowed to stand for about 1 hour, and after confirming that the reaction solution had hardened in a jelly form, it was sealed with a polyvinylidene chloride film to prevent drying. Thereafter, the gelation was allowed to proceed for 1 day. Thereafter, it was removed from the mold, immersed in ethanol, and left for one day or longer. In order to completely remove water and ammonia remaining in the gel, ethanol was replaced twice thereafter.
（３）チタニア被覆シリカウエットゲルの作製
作製したシリカウエットゲルにチタニア被覆を行うため、シリカウエットゲルをトルエンに浸して１日以上放置した。ゲル中に残存するエタノールを完全に除去するため、その後、トルエンの取替えを３回行った。トルエンに対してチタンテトライソプロポキシド（ＴＴＩＰ）を１０ｗｔ％加えた溶液に、トルエン置換を行ったシリカウエットゲルを浸して２４時間放置した。余分なＴＴＩＰを除去するため、その後、トルエンの取替えを３〜４回行った。
(3) Preparation of titania-coated silica wet gel In order to perform titania coating on the prepared silica wet gel, the silica wet gel was immersed in toluene and allowed to stand for 1 day or longer. In order to completely remove ethanol remaining in the gel, toluene was replaced three times thereafter. A silica wet gel subjected to toluene substitution was immersed in a solution obtained by adding 10 wt% of titanium tetraisopropoxide (TTIP) to toluene, and left for 24 hours. To remove excess TTIP, the toluene was then replaced 3-4 times.
（４）チタニア被覆シリカエアロゲルの作製
上記のようにして得られたチタニア被覆シリカウエットゲル担持体を、トルエンを満たしたオートクレーブ中に入れ、トルエンを満たした。ゲルの液相部を液化炭酸ガス（臨界温度３１．１℃、臨界圧力７２．９気圧）に置換するため、加圧ポンプで加圧しながら、液化炭酸ガスをオートクレーブ内に注入した。９０気圧になったとき、気圧を保つようにバルブを調節し、２０℃で２時間保持した。完全に置換するために、置換操作は３回行った。３回目の置換が終わった後にバルブを閉め、オートクレーブの中の気圧を保持した。オートクレーブの温度を上昇させ、圧力を１００気圧に上昇させた。その後、バルブを調節し、圧力を保持した。試料の温度が４０℃を超えたところで、気圧を１気圧／分の速度で減少するように、オートクレーブ内の炭酸ガスを抜き去った。上記手順により作製したチタニア被覆シリカエアロゲル担持体の写真を図１に示す。また、粉砕及び分級により粒度を揃えたチタニア被覆シリカエアロゲル担持体の写真を図２に示す。
(4) Production of titania-coated silica aerogel The titania-coated silica wet gel carrier obtained as described above was placed in an autoclave filled with toluene and filled with toluene. In order to replace the liquid phase part of the gel with liquefied carbon dioxide gas (critical temperature 31.1 ° C., critical pressure 72.9 atm), liquefied carbon dioxide gas was injected into the autoclave while being pressurized with a pressure pump. When the pressure reached 90 atm, the valve was adjusted so as to maintain the atmospheric pressure and maintained at 20 ° C. for 2 hours. In order to completely substitute, the substitution operation was performed three times. After the third replacement, the valve was closed to maintain the pressure in the autoclave. The temperature of the autoclave was raised and the pressure was raised to 100 atmospheres. Thereafter, the valve was adjusted to maintain the pressure. When the temperature of the sample exceeded 40 ° C., the carbon dioxide gas in the autoclave was removed so that the pressure was decreased at a rate of 1 atm / min. A photograph of the titania-coated silica airgel carrier produced by the above procedure is shown in FIG. Moreover, the photograph of the titania-coated silica airgel carrier having a uniform particle size by pulverization and classification is shown in FIG.
（５）金超微粒子のチタニア被覆シリカエアロゲルへの吸着
作製したチタニア被覆シリカエアロゲルを熱処理し、ゲル表面のチオール分子の脱離を行った。その後、作製した金超微粒子にトルエンを加えたトルエン溶液（濃度：Ａｕ１０ｍｇ／１０ｍｌ）に粒度を揃えたチタニア被覆シリカエアロゲルを１００ｍｇ浸した。３０分間攪拌すると、溶液中の金超微粒子が完全にチタニア被覆シリカエアロゲルに吸着された。得られた多孔質複合体の写真を図３に示す。
(5) Adsorption of gold ultrafine particles onto titania-coated silica airgel The produced titania-coated silica airgel was heat-treated to desorb thiol molecules on the gel surface. Thereafter, 100 mg of titania-coated silica aerogel having a uniform particle size was immersed in a toluene solution (concentration: Au 10 mg / 10 ml) obtained by adding toluene to the prepared ultrafine gold particles. After stirring for 30 minutes, the ultrafine gold particles in the solution were completely adsorbed on the titania-coated silica airgel. A photograph of the obtained porous composite is shown in FIG.
（６）多孔質触媒の作製
作製したチタニア被覆シリカエアロゲル担持体を熱分析したところ、約２９０℃においてチオール分子の脱離に対応する重量減少が観測された。このデータを基に、空気雰囲気中（流量：２０ｍｌ／ｍｉｎ）、４００℃で４時間、多孔質複合体を熱処理した。熱処理後のゲルは目視において、熱処理前のものと色の変化はなく、熱処理による粒子径の変化はほとんどないものと考えられる。得られた多孔質触媒の写真を図４、ＴＥＭ観察画像を図５に示す。
(6) Production of porous catalyst When the produced titania-coated silica airgel carrier was subjected to thermal analysis, a weight loss corresponding to desorption of thiol molecules was observed at about 290 ° C. Based on this data, the porous composite was heat-treated at 400 ° C. for 4 hours in an air atmosphere (flow rate: 20 ml / min). It is considered that the gel after the heat treatment is not visually changed from the color before the heat treatment, and the particle diameter is hardly changed by the heat treatment. The photograph of the obtained porous catalyst is shown in FIG. 4, and the TEM observation image is shown in FIG.
（１）チタニア被覆シリカキセロゲルの作製
本実施例では、実施例１の方法により作製したチタニア被覆シリカウエットゲル担持体を、自然乾燥することにより、キセロゲル担持体を得た。実施例１の方法により作製したチタニア被覆シリカウエットゲル担持体を、網ごとガラスシャーレに入れ、室温にて１日以上放置した。その後、６０℃乾燥機にて１日以上放置した。以上の手順により作製したチタニア被覆シリカキセロゲル担持体の写真を図６に示す。また、粉砕及び分級により粒度を揃えたチタニア被覆シリカキセロゲル担持体の写真を図７に示す。
(1) Production of titania-coated silica xerogel In this example, the titania-coated silica wet gel carrier produced by the method of Example 1 was naturally dried to obtain a xerogel carrier. The titania-coated silica wet gel carrier produced by the method of Example 1 was placed in a glass petri dish together with a net and allowed to stand at room temperature for 1 day or longer. After that, it was left in a 60 ° C. dryer for 1 day or longer. A photograph of the titania-coated silica xerogel carrier produced by the above procedure is shown in FIG. Further, a photograph of a titania-coated silica xerogel carrier having a uniform particle size by pulverization and classification is shown in FIG.
（２）金超微粒子のチタニア被覆シリカキセロゲルへの吸着
作製したチタニア被覆シリカキセロゲルを熱処理し、ゲル表面のチオール分子の脱離を行った。その後、実施例１の方法より作製した金超微粒子にトルエンを加えたトルエン溶液（濃度：Ａｕ１０ｍｇ／１０ｍｌ）に粒度を揃えたチタニア被覆シリカキセロゲルを１００ｍｇ浸した。３０分間攪拌すると、溶液中の金超微粒子が完全にチタニア被覆シリカエアロゲルに吸着された。得られた多孔質複合体の写真を図８に示す。
(2) Adsorption of gold ultrafine particles onto titania-coated silica xerogel The prepared titania-coated silica xerogel was heat-treated to desorb thiol molecules on the gel surface. Thereafter, 100 mg of titania-coated silica xerogel having a uniform particle size was immersed in a toluene solution (concentration: Au 10 mg / 10 ml) in which toluene was added to the ultrafine gold particles produced by the method of Example 1. After stirring for 30 minutes, the ultrafine gold particles in the solution were completely adsorbed on the titania-coated silica airgel. A photograph of the obtained porous composite is shown in FIG.
（３）多孔質触媒の作製
作製したチタニア被覆キセロゲル担持体を熱分析したところ、約２９０℃においてチオール分子の脱離に対応する重量減少が観測された。このデータを基に、空気雰囲気中（流量：２０ｍｌ／ｍｉｎ）、４００℃で４時間、多孔質複合体を熱処理した。熱処理後のゲルは目視において、熱処理のものと色の変化はなく、熱処理による粒子径の変化はほとんどないものと考えられる。得られた多孔質触媒の写真を図９、ＴＥＭ観察画像を図１０に示す。
(3) Production of porous catalyst When the produced titania-coated xerogel support was subjected to thermal analysis, a weight loss corresponding to desorption of thiol molecules was observed at about 290 ° C. Based on this data, the porous composite was heat-treated at 400 ° C. for 4 hours in an air atmosphere (flow rate: 20 ml / min). It is considered that the gel after the heat treatment does not change in color from that of the heat-treated gel and there is almost no change in the particle diameter due to the heat treatment. A photograph of the obtained porous catalyst is shown in FIG. 9, and a TEM observation image is shown in FIG.
実施例１の多孔質触媒作製法と同様に、金超微粒子１０ｍｇにトルエン１０ｍｌを加えた濃度のトルエン溶液に、熱処理したチタニア被覆エアロゲル担持体２００ｍｇを投入し、３０分間攪拌後、溶媒の除去及び乾燥を行い、多孔質複合体を作製した。これを４００℃で４時間熱処理し、多孔質触媒を作製した。上記多孔質触媒１００ｍｇに、一酸化炭素を１容量％含む空気混合ガスを１０ｍｌ／ｍｉｎで流通させて、一酸化炭素に対する酸化活性を調べた。その結果、−６０℃で３１．５％、−５５℃で４２％、−５０℃で６６％、−４０℃で１００％、−４０℃以上で１００％の酸化反応率を示し、本発明の多孔質触媒は、低温から常温で高い一酸化炭素酸化活性を示すことが明らかとなった。この結果をグラフに示したものを図１１に示す。 As in the porous catalyst preparation method of Example 1, 200 mg of a heat-treated titania-coated airgel carrier was added to a toluene solution having a concentration of 10 mg of ultrafine gold particles and 10 ml of toluene. After stirring for 30 minutes, removal of the solvent and Drying was performed to prepare a porous composite. This was heat-treated at 400 ° C. for 4 hours to produce a porous catalyst. An air mixed gas containing 1% by volume of carbon monoxide was passed through 100 mg of the porous catalyst at 10 ml / min, and the oxidation activity for carbon monoxide was examined. As a result, the oxidation reaction rate was 31.5% at -60 ° C, 42% at -55 ° C, 66% at -50 ° C, 100% at -40 ° C, and 100% at -40 ° C or higher. It was revealed that the porous catalyst exhibits high carbon monoxide oxidation activity from low temperature to normal temperature. The result is shown in a graph in FIG.
実施例２の多孔質触媒作製法と同様に、金超微粒子１０ｍｇにトルエン１０ｍｌを加えた濃度のトルエン溶液に、熱処理したチタニア被覆キセロゲル担持体２００ｍｇを投入し、３０分間攪拌後、溶媒の除去及び乾燥を行い、多孔質複合体を作製した。これを４００℃で４時間熱処理し、多孔質触媒を作製した。上記多孔質触媒１００ｍｇに、一酸化炭素を１容量％含む空気混合ガスを１０ｍｌ／ｍｉｎで流通させて、一酸化炭素に対する酸化活性を調べた。その結果、−５５℃で３５％、−５０℃で５０％、−４５℃で７５％、−４０℃で１００％、−４０℃以上１００％の酸化反応率を示し、本発明の多孔質触媒は、低温から常温で高い一酸化炭素酸化活性を示すことが明らかとなった。この結果をグラフに示したものを図１２に示す。 As in the porous catalyst preparation method of Example 2, 200 mg of a heat-treated titania-coated xerogel support was added to a toluene solution having a concentration of 10 mg of ultrafine gold particles and 10 ml of toluene. After stirring for 30 minutes, the solvent was removed and Drying was performed to prepare a porous composite. This was heat-treated at 400 ° C. for 4 hours to produce a porous catalyst. An air mixed gas containing 1% by volume of carbon monoxide was passed through 100 mg of the porous catalyst at 10 ml / min, and the oxidation activity for carbon monoxide was examined. As a result, the porous catalyst of the present invention showed an oxidation reaction rate of 35% at -55 ° C, 50% at -50 ° C, 75% at -45 ° C, 100% at -40 ° C, and 100% at -40 ° C or higher. Was found to exhibit high carbon monoxide oxidation activity from low temperature to normal temperature. The result is shown in a graph in FIG.
実施例１の多孔質触媒作製法と同様で、金超微粒子の粒子径を１〜５ｎｍに制御し、それぞれトルエンに溶解した。そこへ、熱処理したチタニア被覆エアロゲル担持体を投入し、３０分間攪拌後、溶媒の除去及び乾燥を行い、多孔質複合体を作製した。これを４００℃で４時間熱処理し、多孔質触媒を作製した。 In the same manner as in the porous catalyst preparation method of Example 1, the particle diameter of the ultrafine gold particles was controlled to 1 to 5 nm, and each was dissolved in toluene. The heat-treated titania-coated airgel carrier was added thereto, and after stirring for 30 minutes, the solvent was removed and dried to prepare a porous composite. This was heat-treated at 400 ° C. for 4 hours to produce a porous catalyst.
上記多孔質触媒１００ｍｇに、一酸化炭素を１容量％含む空気混合ガスを１０ｍｌ／ｍｉｎで流通させて、一酸化炭素に対する酸化活性を調べた。その結果、金超微粒子の平均粒径によって一酸化炭素に対する酸化活性に違いを示すことが明らかとなった。金超微粒子の平均粒径とＴＯＦ（＝単位時間に酸化する一酸化炭素分子の数／金超微粒子表面の金原子の数）の関係をグラフに示したものを図１３に示す。 An air mixed gas containing 1% by volume of carbon monoxide was passed through 100 mg of the porous catalyst at 10 ml / min, and the oxidation activity for carbon monoxide was examined. As a result, it became clear that the oxidation activity for carbon monoxide shows a difference depending on the average particle size of the ultrafine gold particles. FIG. 13 is a graph showing the relationship between the average particle size of gold ultrafine particles and TOF (= number of carbon monoxide molecules oxidized per unit time / number of gold atoms on the surface of gold ultrafine particles).
実施例３で作製した多孔質触媒１００ｍｇを３Ｌのテドラーバックに設置し、ホルムアルデヒド２０ｐｐｍを含む空気ガスを充填し、３０℃恒温槽内に設置し、ホルムアルデヒドの濃度変化及びホルムアルデヒド分解生成物の測定を行った。その結果、分解生成物であるギ酸が検出されなかったことから、部分酸化反応ではなく、分解反応が生じていると考えられる。この結果を表１（多孔質触媒、チタニア被覆シリカエアロゲル・金超微粒子５ｗｔ％多孔質複合体、のホルムアルデヒド分解反応）に示す。 100 mg of the porous catalyst prepared in Example 3 was placed in a 3 L Tedlar bag, filled with air gas containing 20 ppm of formaldehyde, placed in a thermostatic bath at 30 ° C., and the concentration change of formaldehyde and formaldehyde decomposition products were measured. It was. As a result, formic acid, which is a decomposition product, was not detected, and it is considered that a decomposition reaction occurred instead of a partial oxidation reaction. The results are shown in Table 1 (formaldehyde decomposition reaction of porous catalyst, titania-coated silica aerogel / gold ultrafine particle 5 wt% porous composite).
実施例４で作製した多孔質触媒１００ｍｇを３Ｌのテドラーバックに設置し、ホルムアルデヒド２０ｐｐｍを含む空気ガスを充填し、３０℃恒温槽内に設置し、ホルムアルデヒドの濃度変化及びホルムアルデヒド分解生成物の測定を行った。その結果、分解生成物であるギ酸が検出されなかったことから、部分酸化反応ではなく、分解反応が生じていると考えられる。この結果を表２（多孔質触媒、チタニア被覆シリカキセロゲル・金超微粒子５ｗｔ％多孔質複合体、のホルムアルデヒド分解反応）に示す。 100 mg of the porous catalyst prepared in Example 4 was placed in a 3 L Tedlar bag, filled with air gas containing 20 ppm of formaldehyde, placed in a thermostatic bath at 30 ° C., and changes in formaldehyde concentration and formaldehyde decomposition products were measured. It was. As a result, formic acid, which is a decomposition product, was not detected, and it is considered that a decomposition reaction occurred instead of a partial oxidation reaction. The results are shown in Table 2 (formaldehyde decomposition reaction of porous catalyst, titania-coated silica xerogel / gold ultrafine particle 5 wt% porous composite).
実施例３で作製した多孔質触媒１００ｍｇを３Ｌのテドラーバックに設置し、アセトアルデヒド２０ｐｐｍを含む空気ガスを充填し、３０℃恒温槽内に設置し、アセトアルデヒドの濃度変化及びアセトアルデヒド分解生成物の測定を行った。その結果、分解生成物である酢酸が検出されなかったことから、部分酸化反応ではなく、分解反応が生じていると考えられる。この結果を表３（多孔質触媒、チタニア被覆シリカエアロゲル・金超微粒子５ｗｔ％多孔質複合体、のアセトアルデヒド分解反応）に示す。 100 mg of the porous catalyst prepared in Example 3 was placed in a 3 L Tedlar bag, filled with air gas containing 20 ppm of acetaldehyde, placed in a thermostatic bath at 30 ° C., and the concentration change of acetaldehyde and acetaldehyde decomposition product were measured. It was. As a result, since acetic acid as a decomposition product was not detected, it is considered that a decomposition reaction occurred instead of a partial oxidation reaction. The results are shown in Table 3 (Acetaldehyde decomposition reaction of a porous catalyst, titania-coated silica airgel / gold ultrafine particle 5 wt% porous composite).
実施例４で作製した多孔質触媒１００ｍｇを３Ｌのテドラーバックに設置し、アセトアルデヒド２０ｐｐｍを含む空気ガスを充填し、３０℃恒温槽内に設置し、アセトアルデヒドの濃度変化及びアセトアルデヒド分解生成物の測定を行った。その結果、分解生成物である酢酸が検出されなかったことから、部分酸化反応ではなく、分解反応が生じていると考えられる。この結果を表４（多孔質触媒、チタニア被覆シリカキセロゲル・金超微粒子５ｗｔ％多孔質複合体、のアセトアルデヒド分解反応）に示す。 100 mg of the porous catalyst produced in Example 4 was placed in a 3 L Tedlar bag, filled with air gas containing 20 ppm of acetaldehyde, placed in a thermostat at 30 ° C., and the concentration change of acetaldehyde and the acetaldehyde decomposition product were measured. It was. As a result, since acetic acid as a decomposition product was not detected, it is considered that a decomposition reaction occurred instead of a partial oxidation reaction. The results are shown in Table 4 (acetaldehyde decomposition reaction of porous catalyst, titania-coated silica xerogel / gold ultrafine particle 5 wt% porous composite).
実施例３で作製した多孔質触媒１００ｍｇを３Ｌのテドラーバックに設置し、トルエン２０ｐｐｍを含む空気ガスを充填し、３０℃恒温槽内に設置し、トルエンの濃度変化を測定した。その結果を表５（多孔質触媒、チタニア被覆シリカエアロゲル・金超微粒子５ｗｔ％多孔質複合体、のトルエン除去反応）に示す。テドラーバック内のガスを全て脱気し、空気のみを充填し、４０℃恒温槽内に設置し、トルエンの脱離を確認したが、全く検出されなかったことから、分解していると考えられる。 100 mg of the porous catalyst produced in Example 3 was placed in a 3 L Tedlar bag, filled with air gas containing 20 ppm of toluene, placed in a 30 ° C. constant temperature bath, and the change in the concentration of toluene was measured. The results are shown in Table 5 (Toluene removal reaction of a porous catalyst, titania-coated silica airgel / gold ultrafine particle 5 wt% porous composite). All the gas in the Tedlar bag was degassed, filled with air only, and placed in a constant temperature bath at 40 ° C., and desorption of toluene was confirmed, but it was considered that it was decomposed because it was not detected at all.
実施例４で作製した多孔質触媒１００ｍｇを３Ｌのテドラーバックに設置し、トルエン２０ｐｐｍを含む空気ガスを充填し、３０℃恒温槽内に設置し、トルエンの濃度変化を測定した。その結果を表６（多孔質触媒、チタニア被覆シリカキセロゲル・金超微粒子５ｗｔ％多孔質複合体、のトルエン除去反応）に示す。テドラーバック内のガスを全て脱気し、空気のみを充填し、４０℃恒温槽内に設置し、トルエンの脱離を確認したが、全く検出されなかったことから、分解していると考えられる。 100 mg of the porous catalyst produced in Example 4 was placed in a 3 L Tedlar bag, filled with air gas containing 20 ppm of toluene, placed in a 30 ° C. constant temperature bath, and the change in the concentration of toluene was measured. The results are shown in Table 6 (Toluene removal reaction of porous catalyst, titania-coated silica xerogel / gold ultrafine particle 5 wt% porous composite). All the gas in the Tedlar bag was degassed, filled with air only, and placed in a constant temperature bath at 40 ° C., and desorption of toluene was confirmed, but it was considered that it was decomposed because it was not detected at all.
以上詳述したように、本発明は、金属超微粒子を担持した多孔質複合体、その活性多孔質複合体からなる触媒、それらの製造方法及びその用途に係るものであり、本発明により、例えば、金属超微粒子の粒子径を標準偏差が２ｎｍ以下という狭い粒径分布範囲に制御した金属超微粒子を安定に担持した複合体を製造することが可能であり、それにより、従来材と比べて、触媒効率を著しく向上させた高い酸化活性等を有する触媒材を提供することができる。本発明は、例えば、酸化触媒、還元触媒、一酸化炭素の除去、医療や食品分野における消毒・殺菌、電子工業におけるフォトニクス材料、などの種々の応用が期待される。本発明の触媒は、具体的には、例えば、室内や自動車社内における空調装置（空気清浄機、エアコン、分煙機など）の空気浄化フィルター、火災防毒マスクのフィルター、化学工場などで用いられる原料ガスからの一酸化炭素除去フィルター、自動車、バイクなどの排ガスからの一酸化炭素除去フィルター、燃料電池の燃料改質による水素製造プロセスにおける一酸化炭素除去フィルターなどの触媒材として有用である。 As described above in detail, the present invention relates to a porous composite carrying ultrafine metal particles, a catalyst comprising the active porous composite, a method for producing them, and an application thereof. In addition, it is possible to produce a composite that stably supports ultrafine metal particles in which the particle size of ultrafine metal particles is controlled within a narrow particle size distribution range with a standard deviation of 2 nm or less. It is possible to provide a catalyst material having high oxidation activity and the like in which the catalyst efficiency is remarkably improved. The present invention is expected to have various applications such as an oxidation catalyst, a reduction catalyst, removal of carbon monoxide, disinfection / sterilization in the medical and food fields, and a photonics material in the electronics industry. Specifically, the catalyst of the present invention is, for example, an air purification filter for an air conditioner (such as an air cleaner, an air conditioner, or a smoke separator) in a room or an automobile, a fire gas mask filter, a raw material used in a chemical factory, etc. It is useful as a catalyst material for carbon monoxide removal filters from gases, carbon monoxide removal filters from exhaust gas from automobiles, motorcycles, etc., and carbon monoxide removal filters in hydrogen production processes by fuel reforming of fuel cells.
Claims (15)
上記担体が、シリカ、アルミナ、チタニア、又はジルコニアの多孔質体の表面に金属酸化物が被覆された構造を有する金属酸化物被覆多孔体からなる表面積２００ｍ ２ ／ｇ以上の乾燥担体から構成され、上記金属超微粒子が、貴金属、及び遷移金属から選択される１種又は複数種であり、上記金属超微粒子が予め作製した金属超微粒子の粒子サイズそのままに上記ナノスケールの金属超微粒子の粒子径の標準偏差が２ｎｍ又はそれ以下の値に制御されて担持されていることを特徴とする多孔質複合体。 A porous composite formed by fixing nanoscale metal ultrafine particles protected with a surface protective substance on a carrier containing a metal oxide in a dispersed state,
The carrier is composed of a dry carrier having a surface area of 200 m 2 / g or more comprising a metal oxide-coated porous body having a structure in which a metal oxide is coated on the surface of a porous body of silica, alumina, titania, or zirconia, The ultrafine metal particles are one or more selected from precious metals and transition metals, and the ultrafine metal particles have the same particle size as the ultrafine metal particles prepared in advance . porous composite standard deviation is characterized that you have been carried is controlled to 2nm or less value.
上記担体が、シリカ、アルミナ、チタニア、又はジルコニアの多孔質体の表面に金属酸化物が被覆された構造を有する金属酸化物被覆多孔体からなる表面積２００ｍ ２ ／ｇ以上の乾燥担体から構成され、上記金属超微粒子が、貴金属、及び遷移金属から選択される１種又は複数種であり、予め所定の形状に揃えた乾燥担体を用いて担持操作を行うことで該乾燥担体に金属超微粒子をその担持量を制御して担持させることにより上記ナノスケールの金属超微粒子の粒子径の標準偏差を２ｎｍ又はそれ以下の値に制御することを特徴とする多孔質複合体の製造方法。 Nanoscale metal ultrafine particles protected with a surface protective substance are heat-treated in a solution to control the particle size, and this is dispersed in a solvent and brought into contact with the carrier to disperse the metal ultrafine particles in the carrier. A method for producing a porous composite by fixing in a state in which
The carrier is composed of a dry carrier having a surface area of 200 m 2 / g or more comprising a metal oxide-coated porous body having a structure in which a metal oxide is coated on the surface of a porous body of silica, alumina, titania, or zirconia, The metal ultrafine particles are one or more selected from precious metals and transition metals, and the carrying operation is performed using a dry carrier having a predetermined shape in advance so that the ultrafine metal particles are added to the dry carrier. method for producing a porous composite which is characterized that you control the 2nm or less value the standard deviation of the particle diameter of the nano-scale ultra-fine metal particles by supporting by controlling the carrying amount.
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| JP5692957B2 (en) * | 2008-03-31 | 2015-04-01 | 西松建設株式会社 | Exhaust gas treatment system and exhaust gas treatment method |
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| JP7000753B2 (en) | 2017-09-08 | 2022-01-19 | 富士フイルムビジネスイノベーション株式会社 | Titanium oxide airgel particles, method for producing titanium oxide airgel particles, composition for forming a photocatalyst, photocatalyst, and structure. |
| US10538434B2 (en) | 2017-09-08 | 2020-01-21 | Fuji Xerox Co., Ltd. | Titanium oxide aerogel particle, photocatalyst forming composition, and photocatalyst |
| US10807070B2 (en) | 2017-09-12 | 2020-10-20 | Fuji Xerox Co., Ltd. | Silica titania composite aerogel particle, photocatalyst forming composition, and photocatalyst |
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