WO2014083772A1 - 金属ナノ粒子複合体の製造方法およびその方法により製造された金属ナノ粒子複合体 - Google Patents
金属ナノ粒子複合体の製造方法およびその方法により製造された金属ナノ粒子複合体 Download PDFInfo
- Publication number
- WO2014083772A1 WO2014083772A1 PCT/JP2013/006491 JP2013006491W WO2014083772A1 WO 2014083772 A1 WO2014083772 A1 WO 2014083772A1 JP 2013006491 W JP2013006491 W JP 2013006491W WO 2014083772 A1 WO2014083772 A1 WO 2014083772A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- pores
- metal
- nanoparticle composite
- porous body
- Prior art date
Links
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 90
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 229
- 229910052759 nickel Inorganic materials 0.000 claims description 113
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 92
- 229910021536 Zeolite Inorganic materials 0.000 claims description 90
- 239000010457 zeolite Substances 0.000 claims description 90
- 239000002131 composite material Substances 0.000 claims description 79
- 125000002524 organometallic group Chemical group 0.000 claims description 62
- 239000002245 particle Substances 0.000 claims description 37
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 19
- 150000004696 coordination complex Chemical class 0.000 abstract 4
- 239000002105 nanoparticle Substances 0.000 description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 41
- 239000003054 catalyst Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 229910021529 ammonia Inorganic materials 0.000 description 23
- 239000001257 hydrogen Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 238000000635 electron micrograph Methods 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 16
- -1 ammonium ions Chemical class 0.000 description 15
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000000629 steam reforming Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 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
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/087—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/103—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/106—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/123—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/163—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7053—A-type
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7207—A-type
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7215—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7407—A-type
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7607—A-type
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7807—A-type
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
-
- 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
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
Definitions
- the present invention relates to a method for producing a metal nanoparticle composite in which metal nanoparticles usable for a catalyst or the like are dispersed, and a metal nanoparticle composite produced by the method.
- metal nanoparticles for example, nickel nanoparticles having nano-size (average particle diameter of 1 to 5 nm), micropores (average pore diameter of 2 nm or less) and mesopores (average pore diameter of 2 to 50 nm) are used.
- An impregnation method is used as a method of dispersing in a porous body (for example, zeolite, mesoporous silica, activated carbon, etc.).
- a porous body in general, is added to an aqueous solution containing a metal element, and moisture is removed by heating or the like to support the compound containing the metal element on the porous body, and then in a reducing atmosphere.
- the supported compound is reduced to a metal by heating at.
- the metal nanoparticles supported by this impregnation method are heated at a high temperature (for example, 300 to 400 ° C.), the metal nanoparticles move, and the metal nanoparticles adhere to each other and solidify. Sintering occurs and the metal nanoparticles become coarse.
- the metal nanoparticle composite in which the coarsened metal nanoparticles are dispersed has a problem that the catalytic ability is lowered because the surface area having catalytic activity is reduced.
- Non-Patent Document 1 can be applied only to noble metals such as platinum and ruthenium, and cannot be applied to base metals having high catalytic ability such as cobalt and nickel. This is because noble metals such as platinum and ruthenium have a lower ionization tendency than hydrogen and can be reduced easily, whereas base metals such as cobalt and nickel have a higher ionization tendency than hydrogen, so reduction from the cation site is not possible. It is difficult and requires a large amount of energy.
- the present invention has been made in view of the above-described problems, and can be applied to metals having high catalytic ability such as cobalt and nickel, and is a metal nanoparticle composite having a wide range of uses as a catalyst. It is an object to provide a production method and a metal nanoparticle composite produced by the method.
- the method for producing a metal nanoparticle composite of the present invention comprises an adsorption step in which an organometallic complex is adsorbed in the pores of the porous body, and a porous body in which the organometallic complex is adsorbed in the pores.
- an adsorption step in which an organometallic complex is adsorbed in the pores of the porous body, and a porous body in which the organometallic complex is adsorbed in the pores.
- ADVANTAGE OF THE INVENTION while suppressing the coarsening of a metal nanoparticle, it can suppress the fall of the catalytic activity of a metal nanoparticle, and can provide the metal nanoparticle composite which has a wide use as a catalyst. become. In addition, it is possible to provide a metal nanoparticle composite having excellent reaction selectivity.
- FIG. 2 is an electron micrograph (TEM photograph) of the metal nanoparticle composite in Example 1.
- FIG. 2 is an electron micrograph (TEM photograph) of zeolite supporting nickel in Comparative Example 1.
- FIG. 2 is an electron micrograph (TEM photograph) of zeolite supporting nickel in Comparative Example 1.
- FIG. 10 is an electron micrograph (TEM photograph) of a zeolite carrying nickel in Comparative Example 3.
- ethanol steam reforming reaction it is a figure which shows the production
- ethanol steam reforming reaction it is a figure which shows the production
- FIG. 4 is an electron micrograph (TEM photograph) of the metal nanoparticle composite in Example 3.
- FIG. 4 is an electron micrograph (TEM photograph) of the metal nanoparticle composite in Example 3.
- FIG. 4 is an electron micrograph (TEM photograph) of the metal nanoparticle composite in Example 3.
- FIG. 4 is an electron micrograph (TEM photograph) of the metal nanoparticle composite in Example 3.
- an electrically neutral organometallic complex is adsorbed into the pores of a porous body, and the organometallic complex molecules are decomposed in the pores, so that the nanosize (
- This is a method for producing a metal nanoparticle composite in which metal nanoparticles having an average particle diameter of 1 to 5 nm are dispersed.
- the metal nanoparticles produced by the method of the present invention have a substantially spherical shape and an average particle diameter of 1 to 5 nm.
- the metal nanoparticles produced by the method of the present invention can be used as, for example, a reforming catalyst that generates hydrogen from hydrocarbons such as alcohol and methane, an ammonia synthesis catalyst, an automobile exhaust gas purification catalyst, and the like. .
- the “average particle diameter” as used herein refers to measuring the particle diameter of about 10 to 50 metal nanoparticles using a microphotograph of the produced metal nanoparticles, and calculating the number average thereof. Is the average particle size.
- the metal constituting the metal nanoparticles is not particularly limited, and noble metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium, osmium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel Base metals having high catalytic ability such as copper and zinc can be used.
- noble metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium, osmium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel
- Base metals having high catalytic ability such as copper and zinc
- alkali metal elements such as lithium, sodium, and potassium, and alkaline earth metal elements such as magnesium can also be used. These metals may be used alone, or two or more of them may be dispersed in the porous body and supported on the pores of the porous body according to the use of the metal nanoparticles described above
- the porous body used in the method of the present invention is selected from the group consisting of zeolite, porous silica, porous alumina, porous aluminosilicate, porous carbon such as activated carbon and carbon nanotube, and MOF (Metal-organic framework). It is preferable to use at least one kind, and since it has high heat resistance and has three-dimensional regular micropores, it is particularly preferable to use zeolite.
- zeolite for example, A-type zeolite, MFI-type zeolite, X-type zeolite, Y-type zeolite, beta-type zeolite, mordenite, etc. can be used, because the pore diameter is large and the pores are three-dimensionally connected.
- X or Y type zeolite is used.
- the average diameter of pores (average pore diameter) of the porous body is preferably 5 nm or less.
- the average diameter of the pores is larger than 5 nm, the metal nanoparticles supported in the pores may easily diffuse and aggregate, and the stability (fixability) of the metal nanoparticles may be reduced. is there.
- the average diameter of the pores is smaller than the molecular diameter of the organometallic complex, there may be a disadvantage that the organometallic complex that is the precursor of the metal nanoparticles is not introduced into the pores. The diameter needs to be larger than the molecular diameter of the organometallic complex.
- FIG. 8 is a diagram for explaining a method for producing a metal nanoparticle composite according to an embodiment of the present invention.
- an electrically neutral organometallic complex is adsorbed in the pores of the porous body, and the organometallic complex molecules are decomposed in the pores, thereby obtaining a nanosize (average particle diameter of 1 to 5 nm).
- the metal nanoparticle composite in which the metal nanoparticles having) are dispersed is produced.
- organometallic complex those that generate a vapor of the organometallic complex at room temperature or by heating are used, and for example, sublimable metallocene, carbonyl complex, and the like can be used.
- an organic nickel complex such as nickelocene (Ni (C 5 H 5 ) 2 ) can be used.
- the compounding amount of the organometallic complex in this step is determined by the pore volume of the porous body and the volume occupied by the organometallic complex adsorbed in the pores.
- the volume in which the organometallic complex occupies the pores is preferably 1 to 100 parts by volume with respect to 100 parts by volume of the pores of the porous body. This is because when the volume occupied by the organometallic complex exceeds 100 parts by volume, the organometallic complex is adsorbed on the outer surface of the porous body, resulting in the formation of coarse particles on the outer surface of the porous body.
- the volume of the organometallic complex occupying the pores is less than 1 volume part of the pore volume, the number of active points of the catalyst is reduced, so the effect as a catalyst is reduced. This is because there are cases in which
- ⁇ Adsorption process> the mixture of the porous body and the organometallic complex is placed in a reaction vessel such as a test tube, the inside of the reaction vessel is depressurized to a predetermined pressure, and the reaction vessel is sealed. Is heated to vaporize the organometallic complex (for example, sublimate), and the organometallic complex is adsorbed in the pores of the porous body (step S2).
- a reaction vessel such as a test tube
- the inside of the reaction vessel is depressurized to a predetermined pressure
- the reaction vessel is sealed. Is heated to vaporize the organometallic complex (for example, sublimate), and the organometallic complex is adsorbed in the pores of the porous body (step S2).
- the treatment time (adsorption time) in this step is preferably in the range of 1 to 24 hours. This is because when the treatment time is less than 1 hour, it may be difficult to uniformly diffuse the organometallic complex with respect to the entire pores of the porous body. When the treatment time is longer than 24 hours, This is because the production efficiency (time efficiency) is reduced because the organometallic complex has already been uniformly diffused over the entire pores of the porous body. That is, by setting the treatment time in this step to 1 to 24 hours, the organometallic complex can be uniformly diffused throughout the pores of the porous body without reducing the production efficiency.
- the treatment temperature in this step can be appropriately set according to the vaporization (sublimation) temperature of the organometallic complex to be used.
- the organic compound of the organometallic complex (the ligand which is an organic component) adsorbed in the pores of the porous body is decomposed to fix the metal ions in the organometallic complex in the pores of the porous body. More specifically, for example, the organic compound of the organometallic complex is decomposed by irradiating the porous body having the organometallic complex adsorbed in the pores with ultraviolet rays for a predetermined time (step S3).
- this process is not essential for producing metal nanoparticles, but by performing this process, it is more homogeneous and highly dispersible.
- Metal nanoparticles can be obtained.
- an organometallic complex that has a sublimation property and is easily vaporized by heating is used, the organometallic complex can be detached from the pores in the decomposition and reduction process described later, and coarse particles can be formed outside the pores.
- a xenon lamp As the ultraviolet light source, a xenon lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or the like can be used.
- the illuminance of ultraviolet rays is preferably set to 1 to 1000 mW / cm 2 at a wavelength of 360 nm. This may cause inconvenience that it is difficult to sufficiently decompose the organic compound of the organometallic complex when the illuminance of ultraviolet rays is less than 1 mW / cm 2 , and when it is greater than 1000 mW / cm 2 , This is because there may be a disadvantage that the production efficiency (energy efficiency) is lowered.
- the ultraviolet irradiation time varies depending on the amount of the sample, the content of the organometallic complex, and the ultraviolet intensity.
- the role of ultraviolet irradiation is to decompose the organic compound of the organometallic complex adsorbed in the pores of the porous body and fix the metal ions in the organometallic complex in the pores of the porous body. It is necessary to irradiate a sufficient amount of ultraviolet rays. Depending on the shape of the sample container and the condition of the sample, it is necessary to stir the sample during UV irradiation and mix it uniformly. When the sample is discolored by ultraviolet irradiation, the sample is irradiated with ultraviolet light until the entire sample is completely discolored.
- the porous body in which the organometallic complex is adsorbed in the pores is adsorbed in the pores of the porous body by heat treatment at a predetermined temperature for a predetermined time in a reducing atmosphere (for example, in a hydrogen atmosphere).
- a reducing atmosphere for example, in a hydrogen atmosphere.
- the organic compound of the organometallic complex is decomposed (step S4), and the metal cation in the organometallic complex is reduced to produce a metal nanoparticle composite in which the metal nanoparticles are supported on the pores of the porous body (step S4).
- step S5 the metal nanoparticle composite in which the metal nanoparticles are supported on the pores of the porous body.
- the organic compound of the organometallic complex remaining in the pores of the porous body is simultaneously decomposed without being decomposed in the organometallic complex decomposition step. Therefore, in the organometallic complex decomposition step, the organic compound can be effectively decomposed even when the organometallic complex remains in the pores of the porous body.
- the heating temperature in the heat treatment is preferably in the range of 100 to 500 ° C. This is because when the heating temperature is less than 100 ° C., the organic compound of the organometallic complex remaining in the pores of the porous body may not be completely decomposed, which is higher than 500 ° C. This is because there may be a disadvantage that the production efficiency (energy efficiency) decreases.
- the heating time in the heat treatment is preferably in the range of 0.5 to 2 hours. This is because if the heating time is less than 0.5 hours, the temperature may become uneven, and it may be difficult to uniformly heat the entire porous body. This is because the porous body is already heated uniformly, which may cause a disadvantage that the production efficiency (time efficiency) is lowered.
- metal nanoparticles can be produced in the pores of the porous body that is a carrier. Therefore, in the reduction treatment step, at a high temperature (eg, 300 to 400 ° C.). Even if it is a case where it heats, the movement of a metal nanoparticle can be suppressed and it can suppress that a metal nanoparticle adheres to each other.
- a high temperature eg, 300 to 400 ° C.
- the high dispersibility of the metal nanoparticles can be maintained at a high temperature, the aggregation and sintering of the metal nanoparticles can be suppressed, and the coarsening of the metal nanoparticles can be suppressed. As a result, it is possible to suppress a decrease in the catalytic ability of the metal nanoparticles.
- the present invention can be applied not only to noble metals such as platinum and ruthenium but also to base metals having high catalytic ability such as cobalt and nickel, so that the metal has a wide range of uses as a catalyst. It becomes possible to provide a nanoparticle composite.
- the metal nanoparticle composite manufactured by the manufacturing method of this invention can confirm that it is the metal nanoparticle composite manufactured by the manufacturing method of this invention by confirming that organic substances, such as carbon, remain
- a method for confirming that organic substances remain in the metal nanoparticle composite for example, a sample is heated in an oxygen atmosphere, and the generated carbon dioxide and water are analyzed with a mass spectrometer or a gas chromatograph. Analytical methods and the like can be mentioned.
- the method for producing metal nanoparticles according to the present invention preferably includes a decomposition step by irradiation with ultraviolet rays.
- the organic metal adsorbed in the pores of the porous body by the decomposition and reduction process performed in a reducing atmosphere (for example, in a hydrogen atmosphere) regardless of the presence or absence of the decomposition process. Since the organic compound of the complex is decomposed into methane (CH 4 ) and the like, the metal cation contained in the organometallic complex is reduced to a metal to become nanoparticles having an average particle diameter of 1 to 5 nm.
- a decomposition step by ultraviolet irradiation nanoparticles that are more uniform and more dispersible can be obtained.
- the vaporized organometallic complex is adsorbed in the pores of the porous body in the adsorption step.
- a liquid organometallic complex may be used instead of the vaporized organometallic complex.
- an organometallic complex ferrocene (Fe (C 5 H 5 ) 2 ) containing iron can be dissolved in an organic solvent and adsorbed in the pores of the zeolite.
- Example 1 (Production of metal nanoparticle (nickel nanoparticle) composite)
- the mixture of the Y-type zeolite and bis (cyclopentadienyl) nickel (II) was put into a quartz test tube (outer diameter: 12 mm, inner diameter: 10 mm, length: 100 mm) as a reaction vessel, After the inside of the test tube was reduced to a pressure of 5 to 7 Pa, the test tube was sealed.
- this test tube is heated at 130 ° C. for 5 hours to sublimate bis (cyclopentadienyl) nickel (II), and bis (cyclopentadienyl) nickel (II) is put into the pores of the zeolite. It was made to adsorb to.
- the zeolite adsorbed with bis (cyclopentadienyl) nickel (II) was irradiated with ultraviolet rays for 72 hours, The organic component of bis (cyclopentadienyl) nickel (II) was decomposed and nickel ions were fixed in the pores of the zeolite.
- the sample tube was shaken every 12 hours to mix the sample.
- the zeolite irradiated with ultraviolet rays is heated in a hydrogen atmosphere at 400 ° C. for 1 hour to reduce the nickel ions fixed in the pores of the zeolite to nickel.
- a nickel nanoparticle composite carrying nickel nanoparticles was prepared.
- the nickel nanoparticle composite obtained in this example was observed with a transmission electron microscope (manufactured by JEOL Ltd., trade name: JEM-2010) having an acceleration voltage of 200 kV.
- the obtained electron micrograph (TEM photograph) is shown in FIG.
- the nickel nanoparticles are uniformly dispersed in the zeolite, and the particle diameter is found to be 5 nm or less.
- the content (filling amount) of nickel in the nickel nanoparticle composite was measured and found to be 1.9% (% by weight).
- Example 2 A nickel nanoparticle composite was prepared in the same manner as in Example 1 except that the amount of bis (cyclopentadienyl) nickel (II), which was the above organic nickel complex, was changed to 82 mg.
- the content of nickel in the nickel nanoparticle composite was measured and found to be 5.9%.
- the nickel nanoparticle composites obtained in Examples 1 and 2 have a reduced specific surface area and pore volume of the zeolite as compared to the reference zeolite. That is, it was suggested that in the nickel nanoparticle composites obtained in Examples 1 and 2, nickel nanoparticles were present in the pores of the zeolite.
- a zeolite carrying nickel was prepared by a general impregnation method. More specifically, first, 0.063 g of nickel chloride (II) hexahydrate (manufactured by SIGMA-ALDRICH) was dissolved in 20 ml of ion-exchanged water.
- the mixture was heated and dried.
- the obtained powder was placed on an alumina boat and heat-treated at 400 ° C. for 3 hours in the air to obtain a sample of Comparative Example 1. Furthermore, in order to reduce the obtained sample, it was heated at 400 ° C. for 30 minutes in a hydrogen atmosphere.
- the nickel particles of Comparative Example 1 are agglomerated on the zeolite, and the particle diameter is larger than 5 nm. In particular, as shown in FIG. 3, the particle diameter is larger than 50 nm. It can be seen that there are some that have been made.
- the content of nickel in the zeolite carrying nickel was measured and found to be 2.2%.
- Comparative Example 2 A nickel-supported zeolite was produced in the same manner as in Comparative Example 1 except that the amount of nickel chloride (II) hexahydrate used was changed to 0.156 g.
- the content of nickel in the zeolite carrying nickel was measured and found to be 5.7%.
- the nickel particles can move freely on the outer surface of the zeolite as compared with the inside of the pores of the zeolite, in Comparative Example 1, the nickel particles adhere to each other and solidify by heating, and are aggregated and sintered. This is considered to be coarse as shown in FIGS.
- the pore volume is remarkably small as the nickel content increases as compared to the reference zeolite.
- the pore volume was hardly changed. It can be seen that the pore volume is comparable.
- Nickel-supported zeolite was produced by the method described in Patent Document 1 described above. More specifically, first, 100 g of X-type zeolite (manufactured by SIGMA-ALDRICH, trade name: Molecular Sieves 13X) is added to 1000 ml of 1M aqueous ammonium acetate solution (manufactured by SIGMA-ALDRICH), and stirred at room temperature for 24 hours. As a result, sodium ions in the zeolite were exchanged with ammonium ions.
- SIGMA-ALDRICH trade name: Molecular Sieves 13X
- the nickel particles of Comparative Example 3 are aggregated on the zeolite and there are coarse nickel particles having a particle diameter of 10 nm to 20 nm.
- quartz wool was placed in a quartz reaction tube (outer diameter: 12 mm, inner diameter: 10 mm), and 100 mg of a nickel nanoparticle composite as a catalyst was filled thereon.
- the sample was reduced at 400 ° C. for 1 hour in a 3% hydrogen stream (flow rate: 30 ml / min, the rest was argon), and then the inside of the apparatus was replaced with argon.
- a 15% by weight ethanol aqueous solution vaporized at 200 ° C. was supplied at a mass space velocity of 40.5 / hour, and argon as a carrier gas was circulated at 10 ml / min while maintaining the sample at 400 ° C. I let you.
- a gas trap manufactured by Shimadzu Corporation, trade name: GC-14B, equipped with a thermal conductivity detector was used to remove moisture contained in the gas after the reaction using a cooling trap (0 ° C.).
- Column: Shimadzu Corporation, trade name: Shincarbon-ST, 2m was used to analyze the composition of the product gas and confirm the generation of hydrogen and ethylene.
- the electron micrograph (TEM photograph) of the nickel nanoparticle composite body after performing the steam reforming reaction of ethanol is shown in FIG.
- the nickel nanoparticles after the steam reforming reaction were uniformly dispersed in the zeolite as in the case of the nickel nanoparticles shown in FIG. 1, and no change was observed in the dispersibility.
- Example 1 the catalytic properties of nickel nanoparticles are included. Thus, it can be seen that a nickel nanoparticle composite having excellent reaction selectivity can be provided.
- Example 2 the nickel content in each sample obtained in Example 1 and Comparative Examples 1 and 2 was measured using a fluorescent X-ray analyzer (trade name: ZSX Primus II, manufactured by RIGAKU Corporation). The results are shown in Table 2.
- the nickel content in the nickel nanoparticle composite of Example 1 is about one-fourth of the nickel content in the nickel-supported zeolite of Comparative Example 3, Since the production efficiency is almost the same (see FIGS. 5 and 6), the hydrogen production efficiency per unit weight of the nickel particles in the nickel nanoparticle composite of Example 1 is the same as that in the zeolite supporting nickel of Comparative Example 2. It can be seen that it is about 4 times the nickel particles.
- the nickel content in the nickel nanoparticle composite of Example 1 is similar to the nickel content in the zeolite supporting nickel of Comparative Example 1, but as described above, the Example In contrast, the nickel particles of Comparative Example 1 have a particle diameter larger than 50 nm, and there is a significant difference in the particle diameter of the nickel particles. It was. Therefore, it can be seen that the thermal stability (dispersibility at high temperature) of the nickel particles of Example 1 is extremely superior to the thermal stability of the nickel particles of Comparative Example 1 produced by a general impregnation method. .
- a nickel-supported zeolite was produced by reduction in a hydrogen atmosphere without performing ultraviolet irradiation. More specifically, a sample was prepared in the same manner as in the above-described Example 1 except that ultraviolet irradiation using the xenon lamp as an ultraviolet light source was not performed.
- nickel nanoparticles in a highly dispersed state with a diameter of 5 nm or less can be obtained even when ultraviolet irradiation is not performed.
- the dispersibility of the nickel particles is inhomogeneous compared to the nickel nanoparticle composite of Example 1. It turns out that it is.
- the organometallic complex was partially decomposed by ultraviolet light irradiation and fixed in the pores of the zeolite, whereas it was irradiated with ultraviolet light.
- the organometallic complex since the organometallic complex is not fixed in the pores of the zeolite, part of the organometallic complex is desorbed from the pores by heating in the decomposition and reduction process, resulting in inhomogeneous dispersibility. It is thought that it became.
- zeolite supporting nickel (sample obtained in Comparative Example 1), nickel supporting alumina (Al 2 O 3 ), and ruthenium supporting zeolite were prepared by a general impregnation method. .
- nickel (II) chloride hexahydrate manufactured by SIGMA-ALDRICH
- alumina manufactured by Aldrich, trade name: Aluminum Oxide nanopowder, ⁇ 50
- TEM nm particle size
- the obtained powder was placed on an alumina boat and heat-treated in the atmosphere at 400 ° C. for 3 hours to obtain a sample of alumina (Al 2 O 3 ) supporting nickel as a comparative example. Furthermore, in order to reduce the obtained sample, it was heated at 400 ° C. for 60 minutes in a hydrogen atmosphere.
- ruthenium chloride manufactured by SIGMA-ALDRICH Co., Ltd., trade name: ruthenium (III) chloride
- the thermal decomposition reaction of ammonia was carried out in a constant volume closed reactor. More specifically, first, the nickel nanoparticle composite obtained in Example 1 (or each sample prepared as the above-mentioned comparative example) in an Inconel sample tube (outer diameter: 12 mm, inner diameter: 10 mm) 100 mg And heated to 500 ° C. in a vacuum. Next, after the sample temperature was stabilized at 500 ° C., 0.100 MPa of ammonia was charged, and the change in pressure accompanying the progress of the reaction was measured for 24 hours.
- the nickel nanoparticle composite obtained in Example 1 has a very excellent catalytic performance as compared with nickel particles supported by a general impregnation method, and is converted into a zeolite by the impregnation method. It was found that the performance was close to that of a supported ruthenium catalyst.
- reaction rate constant ammonia decomposition rate at the initial stage until the partial pressure of ammonia decreased from 1 to 0.9 was calculated.
- Table 3 The above results are shown in Table 3.
- the nickel nanoparticle composite obtained in Example 1 exhibits a decomposition rate of about 5 to 10 times that of nickel particles supported by a general impregnation method. .
- Example 14 when the nickel nanoparticle composite obtained in Example 1 was used as a catalyst, it was found that excellent catalytic activity could be maintained even when the ammonia decomposition reaction was repeated. .
- FIG. 16 shows an electron micrograph (TEM photograph) of the nickel nanoparticle composite after the above ammonia decomposition reaction was performed seven times.
- the mixture of Y-type zeolite and bis (cyclopentadienyl) cobalt (II) was placed in a quartz test tube (outer diameter: 12 mm, inner diameter: 10 mm, length: 100 mm) as a reaction vessel, After the inside of the test tube was reduced to a pressure of 5 to 7 Pa, the test tube was sealed.
- this test tube is heated at 130 ° C. for 8 hours to sublimate bis (cyclopentadienyl) cobalt (II), and bis (cyclopentadienyl) cobalt (II) is contained in the pores of the zeolite. It was made to adsorb to.
- test tube sealed under reduced pressure was opened in the atmosphere, and the inside of the test tube was exposed to the atmosphere.
- the zeolite adsorbed with bis (cyclopentadienyl) cobalt (II) was irradiated with ultraviolet rays for 72 hours,
- the organic component of bis (cyclopentadienyl) cobalt (II) was decomposed to fix cobalt ions in the pores of the zeolite.
- the zeolite irradiated with ultraviolet rays is heated in a hydrogen atmosphere at 400 ° C. for 1 hour to reduce the cobalt ions fixed in the pores of the zeolite to cobalt, thereby forming the zeolite pores.
- a cobalt nanoparticle composite carrying cobalt nanoparticles was prepared.
- the cobalt nanoparticle composite obtained in this example was observed with a transmission electron microscope (manufactured by JEOL Ltd., trade name: JEM-2010) having an acceleration voltage of 200 kV.
- the obtained electron micrographs (TEM photographs) are shown in FIGS.
- the cobalt nanoparticles are uniformly dispersed in the zeolite, and the particle diameter is as follows. It can be seen that it is 5 nm or less.
- the present invention is suitable for a method for producing a metal nanoparticle composite in which metal nanoparticles usable for a catalyst or the like are dispersed, and a metal nanoparticle composite produced by the method.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Nanotechnology (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
まず、上述の多孔体を加熱して、多孔体に吸着した吸着水を除去した後、この多孔体と有機金属錯体とを均一に混合する(ステップS1)。
次に、多孔体と有機金属錯体との混合体を、試験管等の反応容器内に入れ、この反応容器の内部を所定の圧力に減圧して反応容器を密封した後、所定時間、所定温度で加熱することにより、有機金属錯体を気化(例えば、昇華)させて、有機金属錯体を多孔体の細孔内に吸着させる(ステップS2)。
次に、多孔体の細孔内に吸着させた有機金属錯体の有機化合物(有機成分である配位子)を分解して、有機金属錯体における金属イオンを多孔体の細孔内に定着させる。より具体的には、例えば、細孔内に有機金属錯体が吸着した多孔体に対して、所定時間、紫外線を照射することにより、有機金属錯体の有機化合物の分解を行う(ステップS3)。
次に、細孔内に有機金属錯体が吸着した多孔体を、還元雰囲気下(例えば、水素雰囲気下)において、所定時間、所定温度で加熱処理することにより、多孔体の細孔内に吸着させた有機金属錯体の有機化合物を分解する(ステップS4)と共に、有機金属錯体における金属カチオンを還元して、多孔体の細孔に金属ナノ粒子が担持された金属ナノ粒子複合体を作製する(ステップS5)。
(金属ナノ粒子(ニッケルナノ粒子)複合体の作製)
Y型ゼオライト(和光純薬(株)製,商品名:合成ゼオライトHS-320粉末ナトリウムY、SiO2/Al2O3=5.5)を、真空中において、600℃で20時間、熱処理し、吸着水を除去した。
上述の有機ニッケル錯体であるビス(シクロペンタジエニル)ニッケル(II)の使用量を82mgに変更したこと以外は、上述の実施例1と同様にして、ニッケルナノ粒子複合体を作製した。
次に、実施例1~2で得られたニッケルナノ粒子複合体におけるゼオライトの比表面積及び細孔容積を算出した。より具体的には、蒸気吸着装置(日本ベル(株)製,商品名:BELSORP 18SP)を使用して、77Kにおける窒素吸脱着測定を行うとともに、BET法を用いた解析により評価した。なお、前処理として、ニッケルナノ粒子複合体を、真空中において、300℃で24時間、加熱した。
一般的な含浸法により、ニッケルを担持したゼオライトを作製した。より具体的には、まず、塩化ニッケル(II)六水和物(SIGMA-ALDRICH製)0.063gを、20mlのイオン交換水に溶解した。
上述の塩化ニッケル(II)六水和物の使用量を0.156gに変更したこと以外は、上述の比較例1と同様にして、ニッケルを担持したゼオライトを作製した。
また、比較例1~2において、実施例1~2と同様にして、還元後の試料の比表面積及び細孔容積評価を行った。以上の結果を表1に示す。表1に示すように、比較例1~2で得られた試料におけるゼオライトの比表面積及び細孔容積は、参考用のゼオライトの比表面積及び細孔容積と同程度であることから、ニッケル粒子はゼオライトの外表面に存在することが示唆された。
上述の特許文献1に記載の方法により、ニッケルを担持したゼオライトを作製した。より具体的には、まず、X型ゼオライト(SIGMA-ALDRICH製,商品名:Molecular Sieves13X)100gを1Mの酢酸アンモニウム水溶液(SIGMA-ALDRICH製)1000ml中に添加し、室温において、24時間、攪拌することにより、ゼオライト中のナトリウムイオンをアンモニウムイオンと交換した。
次いで、固定床流動型の反応装置を使用して、実施例1で得られたニッケルナノ粒子複合体によるエタノールの水蒸気改質反応(反応時間:6時間)を行い、実施例1で得られたニッケルナノ粒子複合体の触媒性能を評価した。
次に、実施例1~2、及び比較例1~3で得られた各試料におけるニッケル含有量を測定した。より具体的には、まず、各試料に含まれる有機物やアニオンを除去するために、各試料を大気中において、600℃で3時間加熱した。
次に、有機ニッケル錯体に紫外線を照射した場合の、有機化合物の構造変化について評価した。より具体的には、有機ニッケル錯体であるビス(シクロペンタジエニル)ニッケル(II)を、反応容器である石英製の試験管(外径:12mm、内径:10mm、長さ:100mm)に入れ、この試験管の内部を5~7Paの圧力に減圧した後、試験管を密封した。次いで、360nmの波長における照度が12mW/cm2であるキセノンランプを紫外線の光源として、ビス(シクロペンタジエニル)ニッケル(II)に対して、72時間、紫外線を照射して、ビス(シクロペンタジエニル)ニッケル(II)の有機成分を分解した。なお、紫外線照射中、12時間毎に、試料管を振とうして、試料の混合を行った。
次いで、定容積の反応容器を使用して、実施例1で得られたニッケルナノ粒子複合体によるアンモニア分解反応を行い、実施例1で得られたニッケルナノ粒子複合体の触媒性能を評価した。
実施例1で得られたニッケルナノ粒子複合体を触媒として使用し、上述のアンモニア分解反応における触媒性能評価を5回繰り返し、長期間の使用による安定性を評価した。なお、各試験の間、試料を室温まで冷却した後、システム内をアルゴンで置換した。以上の結果を図14に示す。
(コバルトナノ粒子複合体の作製)
Y型ゼオライト(和光純薬(株)製,商品名:合成ゼオライトHS-320粉末ナトリウムY、SiO2/Al2O3=5.5)を、真空中において、600℃で20時間、熱処理し、吸着水を除去した。
Claims (11)
- 多孔体の細孔に金属ナノ粒子が担持された金属ナノ粒子複合体の製造方法であって、
有機金属錯体を前記多孔体の細孔内に吸着させる吸着工程と、
前記細孔内に前記有機金属錯体が吸着した前記多孔体に対して、還元雰囲気下において、加熱処理を行うことにより、前記多孔体の細孔内に吸着させた前記有機金属錯体の有機化合物を分解すると共に、前記有機金属錯体における金属カチオンを還元して、多孔体の細孔に金属ナノ粒子を担持させる分解還元工程と
を少なくとも備えることを特徴とする金属ナノ粒子複合体の製造方法。 - 前記吸着工程の後であって、前記分解還元工程の前に、前記細孔内に前記有機金属錯体が吸着した前記多孔体に対して、紫外線を照射することにより、前記多孔体の細孔内に吸着させた前記有機金属錯体の有機化合物を分解する分解工程を更に備えることを特徴とする請求項1に記載の金属ナノ粒子複合体の製造方法。
- 前記分解工程において、前記紫外線の照度が、360nmの波長において1~1000mW/cm2であることを特徴とする請求項2に記載の金属ナノ粒子複合体の製造方法。
- 前記吸着工程において、処理時間が1~24時間であることを特徴とする請求項1~請求項3のいずれか1項に記載の金属ナノ粒子複合体の製造方法。
- 前記分解還元工程において、加熱処理温度が100~500℃であることを特徴とする請求項1~請求項4のいずれか1項に記載の金属ナノ粒子複合体の製造方法。
- 前記分解還元工程において、加熱処理時間が0.5~2時間であることを特徴とする請求項1~請求項5のいずれか1項に記載の金属ナノ粒子複合体の製造方法。
- 前記金属ナノ粒子を構成する金属が、チタン、バナジウム、マンガン、鉄、コバルト、及びニッケルからなる群より選ばれる少なくとも1種であることを特徴とする請求項1~請求項6のいずれか1項に記載の金属ナノ粒子複合体の製造方法。
- 前記多孔体が、ゼオライト、多孔質シリカ、多孔質アルミナ、多孔質炭素、及びMOF(Metal-organic framework)からなる群より選ばれる少なくとも1種であることを特徴とする請求項1~請求項7のいずれか1項に記載の金属ナノ粒子複合体の製造方法。
- 前記金属ナノ粒子の平均粒子径が1~5nmであることを特徴とする請求項1~請求項8のいずれか1項に記載の金属ナノ粒子複合体の製造方法。
- 前記細孔の平均径が5nm以下であることを特徴とする請求項1~請求項9のいずれか1項に記載の金属ナノ粒子複合体の製造方法。
- 請求項1~請求項10のいずれか1項に記載の製造方法により製造された金属ナノ粒子複合体。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014549783A JP6284197B2 (ja) | 2012-11-30 | 2013-11-01 | 金属ナノ粒子複合体の製造方法およびその方法により製造された金属ナノ粒子複合体 |
US14/646,349 US9931623B2 (en) | 2012-11-30 | 2013-11-01 | Method for producing metal nanoparticle complex, and metal nanoparticle complex produced by said method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-263374 | 2012-11-30 | ||
JP2012263374 | 2012-11-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014083772A1 true WO2014083772A1 (ja) | 2014-06-05 |
Family
ID=50827436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/006491 WO2014083772A1 (ja) | 2012-11-30 | 2013-11-01 | 金属ナノ粒子複合体の製造方法およびその方法により製造された金属ナノ粒子複合体 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9931623B2 (ja) |
JP (1) | JP6284197B2 (ja) |
WO (1) | WO2014083772A1 (ja) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016064407A (ja) * | 2014-09-16 | 2016-04-28 | 国立大学法人山梨大学 | アンモニア分解触媒とその製造方法および、これを用いた装置 |
WO2017115767A1 (ja) * | 2015-12-28 | 2017-07-06 | トヨタ自動車株式会社 | クラスター担持触媒及びその製造方法 |
CN108387668A (zh) * | 2018-05-04 | 2018-08-10 | 清华大学 | 一种颗粒有机物在线富集解析装置及其使用方法 |
WO2018221707A1 (ja) * | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | 水蒸気改質用触媒構造体、該水蒸気改質用触媒構造体を備える改質装置、及び水蒸気改質用触媒構造体の製造方法 |
WO2018221697A1 (ja) * | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | 合成ガス製造用触媒構造体、該合成ガス製造用触媒構造体を備える合成ガス製造装置及び合成ガス製造用触媒構造体の製造方法 |
WO2018221699A1 (ja) * | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | アンモニア合成触媒構造体及びその製造方法、アンモニア合成装置並びにアンモニアの合成方法 |
JP2019177381A (ja) * | 2019-07-30 | 2019-10-17 | 国立大学法人 大分大学 | アンモニア酸化分解−水素生成触媒、及び水素製造装置 |
JP2020065968A (ja) * | 2018-10-23 | 2020-04-30 | Jxtgエネルギー株式会社 | 触媒、触媒の製造方法、及び合成ガスの製造方法 |
JP2021519204A (ja) * | 2018-03-26 | 2021-08-10 | リサーチ トライアングル インスティテュート | メソポーラス材料内に閉じ込められたナノ触媒を作製する方法およびその使用 |
US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
US11547987B2 (en) | 2017-05-31 | 2023-01-10 | Furukawa Electric Co., Ltd. | Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method |
US11648542B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
US11648538B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
US11648543B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
US11654422B2 (en) | 2017-05-31 | 2023-05-23 | Furukawa Electric Co., Ltd. | Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization |
US11655157B2 (en) | 2017-05-31 | 2023-05-23 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
US11666894B2 (en) | 2017-05-31 | 2023-06-06 | Furukawa Electric Co., Ltd. | Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water |
US11680211B2 (en) | 2017-05-31 | 2023-06-20 | Furukawa Electric Co., Ltd. | Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization |
US11684909B2 (en) | 2017-05-31 | 2023-06-27 | Furukawa Electric Co., Ltd. | Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20230416154A1 (en) * | 2022-06-28 | 2023-12-28 | Entegris, Inc. | De-powdering of green samples using freezing method for additive manufacturing |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008212872A (ja) * | 2007-03-06 | 2008-09-18 | Osaka Univ | 触媒およびその製造方法ならびに過酸化水素の製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5849652A (en) * | 1994-03-14 | 1998-12-15 | Northeastern University | Metal containing catalysts and methods for making same |
DE102005037893A1 (de) * | 2005-08-10 | 2007-02-15 | Süd-Chemie AG | Verfahren zur Herstellung hochaktiver Metall/Metalloxid-Katalysatoren |
WO2007104798A2 (en) * | 2006-03-15 | 2007-09-20 | University Of York | Mesoporous carbonaceous materials, preparation and use thereof |
EP2086674B1 (en) * | 2006-11-17 | 2011-10-05 | Dow Global Technologies LLC | Hydro-oxidation process using a catalyst prepared from a gold cluster complex |
JP5428018B2 (ja) | 2007-08-23 | 2014-02-26 | 栃木県 | ゼオライトxに分散する金属ナノ粒子、金属ナノ粒子分散ゼオライトxおよび金属ナノ粒子分散ゼオライトxの製造方法 |
JP5329463B2 (ja) * | 2009-03-18 | 2013-10-30 | オルガノ株式会社 | 過酸化水素分解処理水の製造方法、過酸化水素分解処理水の製造装置、処理槽、超純水の製造方法、超純水の製造装置、水素溶解水の製造方法、水素溶解水の製造装置、オゾン溶解水の製造方法、オゾン溶解水の製造装置および電子部品の洗浄方法 |
JP5446400B2 (ja) * | 2009-04-03 | 2014-03-19 | 栗田工業株式会社 | 過酸化水素水処理装置 |
US9192919B2 (en) * | 2013-03-14 | 2015-11-24 | Uchicago Argonne, Llc | Selective alkane activation with single-site atoms on amorphous support |
-
2013
- 2013-11-01 WO PCT/JP2013/006491 patent/WO2014083772A1/ja active Application Filing
- 2013-11-01 JP JP2014549783A patent/JP6284197B2/ja not_active Expired - Fee Related
- 2013-11-01 US US14/646,349 patent/US9931623B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008212872A (ja) * | 2007-03-06 | 2008-09-18 | Osaka Univ | 触媒およびその製造方法ならびに過酸化水素の製造方法 |
Non-Patent Citations (4)
Title |
---|
L. STIEVANO ET AL.: "Synthesis and Characterisation of Highly Dispersed Ni/Si02 Catalysts Prepared by Gas-Phase Impregnation/ Decomposition(GPI/D) of a Ni(II) p-Diketonate Precursor Complex", CATALYSIS LETTERS, vol. 100, no. 3-4, April 2005 (2005-04-01), pages 169 - 176 * |
R. MOLINA ET AL.: "a-Alumina-Supported Nickel Catalysts Prepared from NickelAcetylacetonate: A TPR Study", JOURNAL OF CATALYSIS, vol. 173, no. ISSUE, 25 January 1998 (1998-01-25), pages 257 - 267 * |
R. MOLINA ET AL.: "a-Alumina-Supported Nickel Catalysts Prepared with Nickel Acetylacetonate. 2. A Study ofthe Thermolysis of the Metal Precursor", J. PHYS. CHEM. B, VOLUME, vol. 103, no. 51, pages 11290 - 11296 * |
T. BEIN ET AL.: "Photolytic and Thermolytic Decomposition Products from Iron Pentacarbonyl Adsorbed on Y Zeolite", ZEOLITES, vol. 5, July 1985 (1985-07-01), pages 240 - 244 * |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016064407A (ja) * | 2014-09-16 | 2016-04-28 | 国立大学法人山梨大学 | アンモニア分解触媒とその製造方法および、これを用いた装置 |
WO2017115767A1 (ja) * | 2015-12-28 | 2017-07-06 | トヨタ自動車株式会社 | クラスター担持触媒及びその製造方法 |
JP6235764B1 (ja) * | 2015-12-28 | 2017-11-22 | トヨタ自動車株式会社 | クラスター担持触媒及びその製造方法 |
US11655157B2 (en) | 2017-05-31 | 2023-05-23 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
JP7328145B2 (ja) | 2017-05-31 | 2023-08-16 | 古河電気工業株式会社 | 水蒸気改質用触媒構造体、該水蒸気改質用触媒構造体を備える改質装置、及び水蒸気改質用触媒構造体の製造方法 |
WO2018221697A1 (ja) * | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | 合成ガス製造用触媒構造体、該合成ガス製造用触媒構造体を備える合成ガス製造装置及び合成ガス製造用触媒構造体の製造方法 |
WO2018221699A1 (ja) * | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | アンモニア合成触媒構造体及びその製造方法、アンモニア合成装置並びにアンモニアの合成方法 |
US11904306B2 (en) | 2017-05-31 | 2024-02-20 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
JPWO2018221707A1 (ja) * | 2017-05-31 | 2020-03-26 | 古河電気工業株式会社 | 水蒸気改質用触媒構造体、該水蒸気改質用触媒構造体を備える改質装置、及び水蒸気改質用触媒構造体の製造方法 |
JPWO2018221699A1 (ja) * | 2017-05-31 | 2020-04-02 | 古河電気工業株式会社 | アンモニア合成触媒構造体及びその製造方法、アンモニア合成装置並びにアンモニアの合成方法 |
JPWO2018221697A1 (ja) * | 2017-05-31 | 2020-04-02 | 古河電気工業株式会社 | 合成ガス製造用触媒構造体、該合成ガス製造用触媒構造体を備える合成ガス製造装置及び合成ガス製造用触媒構造体の製造方法 |
JP7382828B2 (ja) | 2017-05-31 | 2023-11-17 | 古河電気工業株式会社 | 合成ガス製造用触媒構造体、該合成ガス製造用触媒構造体を備える合成ガス製造装置及び合成ガス製造用触媒構造体の製造方法 |
JP7282026B2 (ja) | 2017-05-31 | 2023-05-26 | 古河電気工業株式会社 | アンモニア合成触媒構造体及びその製造方法、アンモニア合成装置並びにアンモニアの合成方法 |
US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
US11547987B2 (en) | 2017-05-31 | 2023-01-10 | Furukawa Electric Co., Ltd. | Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method |
US11684909B2 (en) | 2017-05-31 | 2023-06-27 | Furukawa Electric Co., Ltd. | Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon |
US11680211B2 (en) | 2017-05-31 | 2023-06-20 | Furukawa Electric Co., Ltd. | Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization |
US11648542B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
US11648538B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
US11648543B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
US11654422B2 (en) | 2017-05-31 | 2023-05-23 | Furukawa Electric Co., Ltd. | Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization |
US11666894B2 (en) | 2017-05-31 | 2023-06-06 | Furukawa Electric Co., Ltd. | Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water |
WO2018221707A1 (ja) * | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | 水蒸気改質用触媒構造体、該水蒸気改質用触媒構造体を備える改質装置、及び水蒸気改質用触媒構造体の製造方法 |
JP7281478B2 (ja) | 2018-03-26 | 2023-05-25 | リサーチ トライアングル インスティテュート | メソポーラス材料内に閉じ込められたナノ触媒を作製する方法およびその使用 |
JP2021519204A (ja) * | 2018-03-26 | 2021-08-10 | リサーチ トライアングル インスティテュート | メソポーラス材料内に閉じ込められたナノ触媒を作製する方法およびその使用 |
CN108387668A (zh) * | 2018-05-04 | 2018-08-10 | 清华大学 | 一种颗粒有机物在线富集解析装置及其使用方法 |
CN108387668B (zh) * | 2018-05-04 | 2023-04-11 | 清华大学 | 一种颗粒有机物在线富集解析装置及其使用方法 |
JP7246040B2 (ja) | 2018-10-23 | 2023-03-27 | Eneos株式会社 | 触媒、触媒の製造方法、及び合成ガスの製造方法 |
JP2020065968A (ja) * | 2018-10-23 | 2020-04-30 | Jxtgエネルギー株式会社 | 触媒、触媒の製造方法、及び合成ガスの製造方法 |
JP2019177381A (ja) * | 2019-07-30 | 2019-10-17 | 国立大学法人 大分大学 | アンモニア酸化分解−水素生成触媒、及び水素製造装置 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2014083772A1 (ja) | 2017-01-05 |
JP6284197B2 (ja) | 2018-03-07 |
US9931623B2 (en) | 2018-04-03 |
US20150290635A1 (en) | 2015-10-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6284197B2 (ja) | 金属ナノ粒子複合体の製造方法およびその方法により製造された金属ナノ粒子複合体 | |
Jafari et al. | Adsorptive removal of toluene and carbon tetrachloride from gas phase using Zeolitic Imidazolate Framework-8: Effects of synthesis method, particle size, and pretreatment of the adsorbent | |
Wang et al. | Hollow ZSM-5 zeolite encapsulated Ag nanoparticles for SO2-resistant selective catalytic oxidation of ammonia to nitrogen | |
Fei et al. | A convenient synthesis of core-shell Co3O4@ ZSM-5 catalysts for the total oxidation of dichloromethane (CH2Cl2) | |
Peng et al. | MnO2-decorated N-doped carbon nanotube with boosted activity for low-temperature oxidation of formaldehyde | |
Ma et al. | Ammonia-treated porous carbon derived from ZIF-8 for enhanced CO2 adsorption | |
Sun et al. | Pt/C@ MnO2 composite hierarchical hollow microspheres for catalytic formaldehyde decomposition at room temperature | |
Huang et al. | Effect of reduction treatment on structural properties of TiO 2 supported Pt nanoparticles and their catalytic activity for formaldehyde oxidation | |
Yin et al. | Thermal stability of ZIF-8 under oxidative and inert environments: A practical perspective on using ZIF-8 as a catalyst support | |
Yang et al. | PdAg alloy nanoparticles encapsulated in N-doped microporous hollow carbon spheres for hydrogenation of CO2 to formate | |
Ertas et al. | Metal-organic framework (MIL-101) stabilized ruthenium nanoparticles: Highly efficient catalytic material in the phenol hydrogenation | |
Li et al. | Integration of an inorganic semiconductor with a metal-organic framework: a platform for enhanced gaseous photocatalytic reactions | |
Petit et al. | Reactive adsorption of acidic gases on MOF/graphite oxide composites | |
Lan et al. | Direct synthesis of mesoporous nitrogen doped Ru-carbon catalysts with semi-embedded Ru nanoparticles for acetylene hydrochlorination | |
Zhang et al. | TiO2 nanorods loaded with AuPt alloy nanoparticles for the photocatalytic oxidation of benzyl alcohol | |
Bharath et al. | Surface functionalized highly porous date seed derived activated carbon and MoS2 nanocomposites for hydrogenation of CO2 into formic acid | |
Gao et al. | Ultrafine PtRu nanoparticles confined in hierarchically porous carbon derived from micro-mesoporous zeolite for enhanced nitroarenes reduction performance | |
Levasseur et al. | Mesoporous silica SBA-15 modified with copper as an efficient NO2 adsorbent at ambient conditions | |
Zhang et al. | Palladium-halloysite nanocomposites as an efficient heterogeneous catalyst for acetylene hydrochlorination | |
Garcia-Garcia et al. | Understanding the role of oxygen surface groups: The key for a smart ruthenium-based carbon-supported heterogeneous catalyst design and synthesis | |
Shang et al. | CO2 capture from wet flue gas using transition metal inserted porphyrin-based metal-organic frameworks as efficient adsorbents | |
Huang et al. | Efficient formaldehyde elimination over Ag/MnO 2 nanorods: Influence of the Ag loading | |
Missaoui et al. | PEG-templated synthesis of ultramicroporous n-ZIF-67 nanoparticles with high selectivity for the adsorption and uptake of CO2 over CH4 and N2 | |
Taghavimoghaddam et al. | SBA-15 supported cobalt oxide species: Synthesis, morphology and catalytic oxidation of cyclohexanol using TBHP | |
Chaparro-Garnica et al. | Efficient production of hydrogen from a valuable CO2-derived molecule: Formic acid dehydrogenation boosted by biomass waste-derived catalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13859054 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 2014549783 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14646349 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13859054 Country of ref document: EP Kind code of ref document: A1 |