JP6048750B2 - Method for producing composite - Google Patents
Method for producing composite Download PDFInfo
- Publication number
- JP6048750B2 JP6048750B2 JP2013104194A JP2013104194A JP6048750B2 JP 6048750 B2 JP6048750 B2 JP 6048750B2 JP 2013104194 A JP2013104194 A JP 2013104194A JP 2013104194 A JP2013104194 A JP 2013104194A JP 6048750 B2 JP6048750 B2 JP 6048750B2
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- JP
- Japan
- Prior art keywords
- metal complex
- inorganic material
- porous metal
- raw material
- treatment
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 150000004696 coordination complex Chemical class 0.000 claims description 86
- 229910010272 inorganic material Inorganic materials 0.000 claims description 78
- 239000011147 inorganic material Substances 0.000 claims description 77
- 239000002994 raw material Substances 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000001556 precipitation Methods 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 23
- 239000013110 organic ligand Substances 0.000 claims description 21
- 230000001376 precipitating effect Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 description 32
- 239000000047 product Substances 0.000 description 30
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 13
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 13
- 238000003917 TEM image Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- -1 biquinoline Chemical compound 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical compound CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 description 2
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 2
- DBZAKQWXICEWNW-UHFFFAOYSA-N 2-acetylpyrazine Chemical compound CC(=O)C1=CN=CC=N1 DBZAKQWXICEWNW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- SVRNCBGWUMMBQB-UHFFFAOYSA-N hydroxyphenazine Natural products C1=CC=C2N=C3C(O)=CC=CC3=NC2=C1 SVRNCBGWUMMBQB-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- HORKYAIEVBUXGM-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoxaline Chemical compound C1=CC=C2NCCNC2=C1 HORKYAIEVBUXGM-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- SILNNFMWIMZVEQ-UHFFFAOYSA-N 1,3-dihydrobenzimidazol-2-one Chemical compound C1=CC=C2NC(O)=NC2=C1 SILNNFMWIMZVEQ-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ABJFBJGGLJVMAQ-UHFFFAOYSA-N 1,4-dihydroquinoxaline-2,3-dione Chemical compound C1=CC=C2NC(=O)C(=O)NC2=C1 ABJFBJGGLJVMAQ-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- ANFXTILBDGTSEG-UHFFFAOYSA-N 1-methyl-4,5-dihydroimidazole Chemical compound CN1CCN=C1 ANFXTILBDGTSEG-UHFFFAOYSA-N 0.000 description 1
- YJBAUTPCBIGXHL-UHFFFAOYSA-N 1-phenyl-4,5-dihydroimidazole Chemical compound C1=NCCN1C1=CC=CC=C1 YJBAUTPCBIGXHL-UHFFFAOYSA-N 0.000 description 1
- XWIYUCRMWCHYJR-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyridine Chemical compound C1=CC=C2NC=CC2=N1 XWIYUCRMWCHYJR-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- FKHNZQFCDGOQGV-UHFFFAOYSA-N 2,3-dimethylquinoxaline Chemical compound C1=CC=C2N=C(C)C(C)=NC2=C1 FKHNZQFCDGOQGV-UHFFFAOYSA-N 0.000 description 1
- RSNQVABHABAKEZ-UHFFFAOYSA-N 2,3-diphenylquinoxaline Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 RSNQVABHABAKEZ-UHFFFAOYSA-N 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- OGSULPWGXWPZOJ-UHFFFAOYSA-N 2-(1,8-naphthyridin-2-yl)-1,8-naphthyridine Chemical compound C1=CC=NC2=NC(C3=NC4=NC=CC=C4C=C3)=CC=C21 OGSULPWGXWPZOJ-UHFFFAOYSA-N 0.000 description 1
- LNJZJDLDXQQJSG-UHFFFAOYSA-N 2-phenylpyrazine Chemical compound C1=CC=CC=C1C1=CN=CC=N1 LNJZJDLDXQQJSG-UHFFFAOYSA-N 0.000 description 1
- OMMPOLDESJSYDZ-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-3,4-diamine Chemical group NC1=CC=NC(C=2N=CC=CC=2)=C1N OMMPOLDESJSYDZ-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SWXRLIIDRHQLAU-UHFFFAOYSA-N N1=CC=C(C=C1)C1=CC=NC=C1.N1=CC=C(C=C1)C1=CC=NC=C1 Chemical group N1=CC=C(C=C1)C1=CC=NC=C1.N1=CC=C(C=C1)C1=CC=NC=C1 SWXRLIIDRHQLAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- PTWPFSLMTOQWLD-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C=1(C(=CC=C2C=CC=CC12)C(=O)O)C(=O)O.C=1(C(=CC=C2C=CC=CC12)C(=O)O)C(=O)O PTWPFSLMTOQWLD-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- INAAIJLSXJJHOZ-UHFFFAOYSA-N pibenzimol Chemical compound C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(=NC4=CC=3)C=3C=CC(O)=CC=3)C2=C1 INAAIJLSXJJHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- XFTQRUTUGRCSGO-UHFFFAOYSA-N pyrazin-2-amine Chemical compound NC1=CN=CC=N1 XFTQRUTUGRCSGO-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
本発明は、多孔性金属錯体と無機材料を含む複合体の製造方法に関する。 The present invention relates to a method for producing a composite comprising a porous metal complex and an inorganic material.
従前より、中心金属とこれに配位する多座有機配位子からなる金属錯体が集積し、多孔性の三次元構造体となった多孔性金属錯体は多数知られている（例えば特許文献１、２）。 Conventionally, many porous metal complexes in which a metal complex composed of a central metal and a multidentate organic ligand coordinated thereto are accumulated to form a porous three-dimensional structure have been known (for example, Patent Document 1). 2).
こうした多孔性金属錯体は、ゼオライトや活性炭といった他の多孔性材料に比べ、均一な細孔を形成することができることから、水素、二酸化炭素、一酸化炭素、酸素、窒素、炭化水素等の吸着材料や吸蔵材料としての利用が期待され、その構造や合成法に関する研究が進められている。 Since such porous metal complexes can form uniform pores compared to other porous materials such as zeolite and activated carbon, adsorbing materials such as hydrogen, carbon dioxide, carbon monoxide, oxygen, nitrogen, hydrocarbons, etc. It is expected to be used as an occlusion material, and research on its structure and synthesis method is underway.
通常、多孔性金属錯体は、金属塩と有機配位子となる化合物をアルコール等の溶媒中に溶解し、反応させて析出（以下「液相法」）させることにより得られるが、液相法による生成には数時間から数日、場合によっては１週間近い時間を要し、また多量の溶媒が必要であった。 Usually, a porous metal complex is obtained by dissolving a metal salt and an organic ligand compound in a solvent such as alcohol and reacting them to precipitate (hereinafter “liquid phase method”). It took several hours to several days, and in some cases nearly one week, and a large amount of solvent was required.
本出願人等は、先に出願した特願２０１１−１２６０９１により、液相法を含む従来例に比べ、極めて短時間で多孔性金属錯体を合成できる製造方法を提供した。また特願２０１１−１２７９２２により、触媒作用を有する機能材料と多孔性金属錯体を含む複合体を合成できる製造方法も提供した。 The present applicants and others provided a manufacturing method capable of synthesizing a porous metal complex in a very short time as compared with the conventional example including the liquid phase method, according to Japanese Patent Application No. 2011-126091 filed earlier. In addition, Japanese Patent Application No. 2011-127922 also provided a production method capable of synthesizing a composite containing a functional material having a catalytic action and a porous metal complex.
本発明は、更に無機材料と多孔性金属錯体を含む複合体の新規な製造方法を提供するものであり、詳しくは、多孔性金属錯体に無機材料が内包された複合体を生成する製造方法を提供するものである。 The present invention further provides a novel method for producing a composite containing an inorganic material and a porous metal complex, and more specifically, a production method for producing a composite in which an inorganic material is included in a porous metal complex. It is to provide.
上記の目的を達成する本願第１発明は、中心金属及び該中心金属に配位する有機配位子を含む有機金属錯体が集積して形成される、多孔性構造を有する多孔性金属錯体と、当該多孔性金属錯体に内包された無機材料を含む複合体の製造方法であって、前記中心金属を含む化合物、前記有機配位子となる化合物、及び、前記無機材料となる化合物が溶解している原料溶液を調製する調製処理と、前記原料溶液から前記多孔性金属錯体と前記無機材料を一度に析出させる析出処理を行うことにより、前記多孔性金属錯体に前記無機材料が内包された複合体を生成することを特徴とする。 The first invention of the present application that achieves the above object comprises a porous metal complex having a porous structure formed by integrating an organic metal complex containing a central metal and an organic ligand coordinated to the central metal, A method for producing a composite including an inorganic material encapsulated in the porous metal complex, wherein the compound including the central metal, the compound serving as the organic ligand, and the compound serving as the inorganic material are dissolved. A composite in which the inorganic material is encapsulated in the porous metal complex by performing a preparation process for preparing the raw material solution and a precipitation process for precipitating the porous metal complex and the inorganic material from the raw material solution at once. Is generated.
また、上記の目的を達成する本願第２発明は、中心金属及び該中心金属に配位する有機配位子を含む有機金属錯体が集積して形成される、多孔性構造を有する多孔性金属錯体と、当該多孔性金属錯体に内包される無機材料を含む複合体の製造方法であって、前記中心金属を含む化合物、前記有機配位子となる化合物、及び、前記無機材料となる化合物が溶解している原料溶液を調製する調製工程と、前記原料溶液から前記多孔性金属錯体を析出させる第１の析出処理と、前記第１の析出処理を行った後、前記無機材料を析出させる第２の析出処理を行うことにより、前記多孔性金属錯体に前記無機材料が内包された複合体を生成することを特徴とする。 The second invention of the present application that achieves the above object is a porous metal complex having a porous structure in which an organic metal complex containing a central metal and an organic ligand coordinated to the central metal is integrated. And a method for producing a composite containing an inorganic material encapsulated in the porous metal complex, wherein the compound containing the central metal, the compound serving as the organic ligand, and the compound serving as the inorganic material are dissolved. A preparation step for preparing the raw material solution, a first precipitation treatment for precipitating the porous metal complex from the raw material solution, and a second precipitating step for the inorganic material after the first precipitation treatment. By performing the precipitation treatment, a composite body in which the inorganic material is included in the porous metal complex is generated.
また、上記の目的を達成する本願第３発明は、中心金属及び該中心金属に配位する有機配位子を含む有機金属錯体が集積して形成される、多孔性構造を有する多孔性金属錯体と、当該多孔性金属錯体に内包される無機材料を含む複合体の製造方法であって、前記中心金属を含む化合物、前記有機配位子となる化合物、及び、前記無機材料となる化合物が溶解している原料溶液を調製する調製工程と、前記原料溶液から前記複合体の前駆体粒子を析出させるプレ析出処理と、前記プレ析出処理を行った後、前記多孔性金属錯体と前記無機材料を析出させる本析出処理を行うことにより、前記多孔性金属錯体に前記無機材料が内包された複合体を生成することを特徴とする。 In addition, the third invention of the present application that achieves the above object is to provide a porous metal complex having a porous structure formed by integrating organic metal complexes including a central metal and an organic ligand coordinated to the central metal. And a method for producing a composite containing an inorganic material encapsulated in the porous metal complex, wherein the compound containing the central metal, the compound serving as the organic ligand, and the compound serving as the inorganic material are dissolved. Preparing the raw material solution, pre-precipitation treatment for precipitating the precursor particles of the composite from the raw material solution, and after performing the pre-precipitation treatment, the porous metal complex and the inorganic material By performing the main precipitation process for precipitation, a composite body in which the inorganic material is included in the porous metal complex is generated.
本発明によれば、多孔性金属錯体と無機材料を含む複合体を極めて短時間に合成することができ、使用する溶媒量を減らすことも可能である。 According to the present invention, a composite containing a porous metal complex and an inorganic material can be synthesized in a very short time, and the amount of solvent used can be reduced.
以下、本発明の製造方法を説明する。 Hereinafter, the production method of the present invention will be described.
先ず、目的とする多孔性金属錯体に応じた金属化合物と、有機配位子となる化合物と、無機材料となる化合物を溶媒に溶解し、均一に分散させて原料溶液の調製を行う。 First, a metal compound corresponding to the target porous metal complex, a compound that becomes an organic ligand, and a compound that becomes an inorganic material are dissolved in a solvent and uniformly dispersed to prepare a raw material solution.
本発明で使用可能な金属化合物は、原料溶液に使用する溶媒に溶解可能なものであり、Ｚｎ、Ｃｕ、Ｍｎ、Ｃｏ、Ｐｄ、Ｍｇ、Ｃａ、Ａｌ、Ｃｒ、Ｍｏ、Ｗ、Ｆｅ、Ｒｕ、Ｒｈ、Ｎｉ、Ｃｄ等の無機化合物や有機化合物を使用することができ、その一例としては酢酸塩、蟻酸塩、硫酸塩、硝酸塩、炭酸塩、塩化物等である。 The metal compound that can be used in the present invention is soluble in the solvent used for the raw material solution, and is Zn, Cu, Mn, Co, Pd, Mg, Ca, Al, Cr, Mo, W, Fe, Ru, Inorganic and organic compounds such as Rh, Ni, and Cd can be used, and examples thereof include acetate, formate, sulfate, nitrate, carbonate, chloride, and the like.
また有機配位子となる化合物も、原料溶液に使用する溶媒に溶解可能であれば特に限定はないが、例えば、ピラジン、アミノピラジン、メチルピラジン、ジメチルピラジン、アセチルピラジン、フェニルピラジン、キノキサリン、テトラヒドロキノキサリン、ジメチルキノキサリン、ジヒドロキシキノキサリン、ジフェニルキノキサリン、フェナジン、ヒドロキシフェナジン、ピリミジン、ナフチリジン、キナゾリン、ビピリジン、ターピリジン、ピロロピリジン、ビキノリン、ビナフチリジン、ビピコリン、ジアミノビピリジル、イミダゾール、メチルイミダゾリン、フェニルイミダゾリン、アミノベンゾイミダゾール、メルカプトベンゾイミダゾール、ヒドロキシベンゾイミダゾール、メチルイミダゾール、ビスベンゾイミダゾール、ビスベンゾチアゾール、ビスベンゾオキサゾールイミダゾール、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ジヒドロキシテレフタル酸、ベンゼントリカルボン酸、ベンゼントリｐ−安息香酸、ビフェニルジカルボン酸等を使用することができる。 The organic ligand compound is not particularly limited as long as it can be dissolved in the solvent used for the raw material solution. For example, pyrazine, aminopyrazine, methylpyrazine, dimethylpyrazine, acetylpyrazine, phenylpyrazine, quinoxaline, tetrahydro Quinoxaline, dimethylquinoxaline, dihydroxyquinoxaline, diphenylquinoxaline, phenazine, hydroxyphenazine, pyrimidine, naphthyridine, quinazoline, bipyridine, terpyridine, pyrrolopyridine, biquinoline, binaphthyridine, bipicoline, diaminobipyridyl, imidazole, methylimidazoline, phenylimidazoline, , Mercaptobenzimidazole, hydroxybenzimidazole, methylimidazole, bisbenzimidazole, Benzothiazole, bisbenzoxazole imidazole, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, dihydroxy terephthalic acid, benzenetricarboxylic acid, benzenetricarboxylic p- acid, can be used biphenyl dicarboxylic acid.
これらを溶解する溶媒としては、最終目的物である複合体を分解しないものであれば使用することができ、例えば、メタノール、エタノール、プロパノール等のアルコール類、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン等のハロゲン化炭化水素、アセトニトリル、テトラヒドロフラン、ジオキサン、ジメチルホルムアミド、ジメチルイミダゾリジノン、スルホラン、アセトン等の有機溶媒、水等が挙げられ、これらを単独若しくは二種以上を混合して使用することができ、特にはジメチルホルムアミド等の配位性溶媒を使用することが好ましい。 Solvents that dissolve them can be used as long as they do not decompose the final target complex, for example, alcohols such as methanol, ethanol, and propanol, and aromatic carbonization such as benzene, toluene, and xylene. Hydrogen, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc., organic solvents such as acetonitrile, tetrahydrofuran, dioxane, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone, etc., water alone etc. Or it can mix and use 2 or more types, It is preferable to use coordinating solvents, such as a dimethylformamide, especially.
これらを用いて得られる多孔性金属錯体の一例としては、［Ｚｎ（１，３−ｂｄｃ）（ｂｐｙ）］、［Ｍｎ（１，４−ｂｄｃ）（ｂｐｙ）］、［Ｚｎ（２ＭｅＩＭ）２］、［Ｚｎ（ｄｏｂｄｃ）］、［Ｚｎ４Ｏ（１，４−ｂｄｃ）３］、［Ｚｎ４Ｏ（２，６−ｎｄｃ）３］、［Ｃｕ３（ｂｔｃ）２］、［Ａｌ（ＯＨ）（１，４−ｂｄｃ）］、［Ａｌ−ＢＴＢ］等があるが、本発明はこれらに限定されるものではない。なお、ここでｂｄｃはｂｅｎｚｅｎｅｄｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ（１，３−ｂｄｃ；イソフタル酸、１，４−ｂｄｃ；テレフタル酸）、ｂｐｙは４，４’−ｂｉｐｙｒｉｄｉｎｅ（４，４’−ビピリジン）、２ＭｅＩＭは２−Ｍｅｔｈｙｌｉｍｉｄａｚｏｌｅ（２メチルイミダゾール）、ｄｏｂｄｃは２，５−ｄｉｈｙｄｒｏｘｙ−１，４−ｂｅｎｚｅｎｅｄｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ（ジヒドロキシテレフタル酸）、ｎｄｃはｎａｐｈｔｈａｌｅｎｅ−ｄｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ（ナフタレンジカルボン酸）、ｂｔｃはｂｅｎｚｅｎｅ−ｔｒｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ（ベンゼントリカルボン酸）、ＢＴＢはｂｅｎｚｅｎｅ−１，３，５−ｔｒｉｓｂｅｎｚｏｉｃ ａｃｉｄ（ベンゼントリｐ−安息香酸）を意味する。 As an example of the porous metal complex obtained using these, [Zn (1,3-bdc) (bpy)], [Mn (1,4-bdc) (bpy)], [Zn (2MeIM) 2 ] , [Zn (dobdc)], [Zn 4 O (1,4-bdc) 3 ], [Zn 4 O (2,6-ndc) 3 ], [Cu 3 (btc) 2 ], [Al (OH) (1,4-bdc)], [Al-BTB], and the like, but the present invention is not limited to these. Here, bdc is benzenical carboxylic acid (1,3-bdc; isophthalic acid, 1,4-bdc; terephthalic acid), bpy is 4,4′-bipyridine (4,4′-bipyridine), and 2MeIM is 2-methylimidazole. (2-methylimidazole), dobdc is 2,5-dihydroxy-1,4-benzenical carboxylic acid (dihydroxyterephthalic acid), ndc is naphthalene-dicarboxylic acid (naphthalenedicarboxylic acid), and btc is benzone-tricaric acid carboxylic acid. BTB means benzone-1,3,5-trisbenzoic acid (benzenetri-p-benzoic acid) Taste.
一方、多孔性金属錯体に内包される無機材料としては特に限定はないが、たとえば、Ｎｉ、Ａｇ、Ｐｄ、Ｐｔ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｃｕ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ及びＩｒ等の少なくとも１種の金属元素からなる金属、合金或いはそれらの複合物や、シリカ、アルミナ、酸化銅、酸化マンガン、酸化チタン、酸化ルテニウム等の金属酸化物、ガラス、セラミックスなどを利用することができる。 On the other hand, the inorganic material included in the porous metal complex is not particularly limited. For example, Ni, Ag, Pd, Pt, Sc, Ti, V, Cr, Mn, Co, Cu, Y, Zr, Nb, Metals, alloys or composites of at least one metal element such as Mo, Tc, Ru, Rh, Ag, Hf, Ta, W, Re, Os and Ir, silica, alumina, copper oxide, manganese oxide Metal oxides such as titanium oxide and ruthenium oxide, glass, ceramics, and the like can be used.
また触媒能を有する無機材料を選択した場合には、本発明により得られる複合体を触媒材料として用いることもできるようになる。 Further, when an inorganic material having catalytic ability is selected, the composite obtained by the present invention can be used as the catalyst material.
本発明は、無機材料が多孔性金属錯体の内部に十分分散された複合体を得るために、後述するように、無機材料を原料溶液から析出させることを特徴とする。そのため、本発明において無機材料は、原料溶液に使用する溶媒に溶解可能な化合物として、前記中心金属を含む化合物、前記有機配位子となる化合物と共に原料溶液中に溶解して含まれる。仮に無機材料が原料溶液中に溶解しない形態で含まれている場合（例えば特願２０１２−６７５４０）、或いは無機材料の原料溶液から析出する場合であっても、それが多孔性金属錯体の析出前に行われ、多孔性金属錯体が析出する前に原料溶液中に無機材料が溶解しない形態で存在する場合には、ナノオーダーサイズの無機材料を内包する本発明の複合体を得ることは難しい。本発明において無機材料は、多孔性金属錯体の析出と同一の析出処理か、或いは多孔性金属錯体の析出処理後の原料溶液からの析出処理で析出するため、容易に、数ｎｍから数百ｎｍ程度の大きさの無機材料が多孔性金属錯体に内包された複合体を得ることができる。 The present invention is characterized in that the inorganic material is precipitated from the raw material solution as described later in order to obtain a composite in which the inorganic material is sufficiently dispersed inside the porous metal complex. Therefore, in the present invention, the inorganic material is dissolved and contained in the raw material solution together with the compound containing the central metal and the compound serving as the organic ligand as a compound that can be dissolved in the solvent used for the raw material solution. Even if the inorganic material is included in the raw material solution in a form that does not dissolve (for example, Japanese Patent Application No. 2012-67540), or even if it is precipitated from the raw material solution of the inorganic material, it is before the porous metal complex is precipitated. In the case where the inorganic material is present in the raw material solution before the porous metal complex is precipitated, it is difficult to obtain the composite of the present invention including the nano-order size inorganic material. In the present invention, the inorganic material is deposited by the same deposition treatment as the deposition of the porous metal complex or by the deposition treatment from the raw material solution after the deposition treatment of the porous metal complex. A composite body in which an inorganic material of a certain size is included in a porous metal complex can be obtained.
無機材料となる化合物としては、原料溶液中に溶解するものであれば特に限定はなく、前述した無機材料の無機化合物や有機化合物を使用することができ、その一例としては酢酸塩、蟻酸塩、硫酸塩、硝酸塩、炭酸塩、塩化物やアセチルアセトナト等である。 The inorganic material compound is not particularly limited as long as it dissolves in the raw material solution, and inorganic compounds and organic compounds of the inorganic material described above can be used. Examples thereof include acetates, formates, Sulfates, nitrates, carbonates, chlorides, acetylacetonates and the like.
本発明の製造方法においては、上述した金属化合物、有機配位子となる化合物、無機材料となる化合物を溶媒に溶解し、均一に攪拌することによって原料溶液を調製する。この際の各原料の配合比率は、目的とする複合体の組成や選択する原料によって適宜設定される。 In the production method of the present invention, the above-described metal compound, compound that becomes an organic ligand, and compound that becomes an inorganic material are dissolved in a solvent, and a raw material solution is prepared by stirring uniformly. The mixing ratio of each raw material at this time is appropriately set depending on the composition of the target complex and the raw material to be selected.
本発明の製造方法においては、その工程において、原料溶液中の金属化合物及び有機配位子となる化合物から多孔性金属錯体が生成される第１の析出反応と、原料溶液中の無機材料となる化合物から無機材料が生成される第２の析出反応が行われる。 In the production method of the present invention, the first precipitation reaction in which a porous metal complex is generated from the metal compound in the raw material solution and the compound that becomes the organic ligand in the process, and the inorganic material in the raw material solution. A second precipitation reaction is performed in which an inorganic material is produced from the compound.
そして本願第１発明においては、前記第１、第２の析出反応を一度の処理工程の中で行い、また本願第２発明においては、前記第１の析出反応と前記第２の析出反応とを異なる処理工程の中で行う。 In the first invention of the present application, the first and second precipitation reactions are performed in one processing step. In the second invention of the present application, the first precipitation reaction and the second precipitation reaction are performed. Perform in different processing steps.
更に、本願第３発明においては、前記第１、第２の析出反応に先だって、目的物である複合体の前駆体粒子を析出させる処理を行う。 Further, in the third invention of the present application, prior to the first and second precipitation reactions, a process for precipitating the precursor particles of the composite as the object is performed.
その結果、本願第１〜３発明は共に、多孔性金属錯体内に無機材料が内包された構造の複合体を効率よく得ることができる。 As a result, both the first to third inventions of the present application can efficiently obtain a composite having a structure in which an inorganic material is encapsulated in a porous metal complex.
特に本願第２〜３発明は、無機材料が多孔性金属錯体内に十分分散し存在している複合体を得やすく、生産効率が特に優れている。 In particular, the second to third inventions of the present application are particularly excellent in production efficiency because it is easy to obtain a composite in which an inorganic material is sufficiently dispersed and present in a porous metal complex.
以下、先ず本願第１発明から説明する。 Hereinafter, the first invention of the present application will be described first.
第１発明においては、前述した原料溶液を調製した後、原料溶液に対して、多孔性金属錯体及び無機材料を一度に析出させる析出処理を行う。 In the first invention, after the raw material solution described above is prepared, a precipitation treatment for precipitating the porous metal complex and the inorganic material at a time is performed on the raw material solution.
多孔性金属錯体及び無機材料を一度に析出させる処理とは、前述した第１の析出反応と第２の析出反応とがほぼ同時に行われる処理であり、少なくとも一回の工程の中で行われる処理である。 The treatment for precipitating the porous metal complex and the inorganic material at a time is a treatment in which the first precipitation reaction and the second precipitation reaction described above are performed almost simultaneously, and a treatment performed in at least one step. It is.
第１発明において具体的な析出処理としては、原料溶液を均一且つ急速に加熱する処理が好ましい。 In the first invention, the specific precipitation treatment is preferably a treatment for heating the raw material solution uniformly and rapidly.
当該析出処理としては、原料溶液を均一且つ急速に加熱できる限り、その手段や方法は公知の加熱手段や加熱方法を利用することができ、特に限定はされないが、特に均一且つ急速に加熱できることからマイクロ波の照射による加熱が好ましい。 As the precipitation treatment, as long as the raw material solution can be uniformly and rapidly heated, the means and method thereof can use known heating means and heating methods, and are not particularly limited, but can be particularly uniformly and rapidly heated. Heating by microwave irradiation is preferred.
目的とする多孔性金属錯体や使用する原料にもよるが、マイクロ波は、１００〜５００℃の温度範囲で加熱するよう制御することが好ましい。加熱温度が５００℃を越えると有機配位子が分解してしまい目的物が得られず、一方、１００℃未満では目的物の生成が不十分である。 Although depending on the target porous metal complex and the raw material to be used, it is preferable to control the microwave to be heated in a temperature range of 100 to 500 ° C. When the heating temperature exceeds 500 ° C., the organic ligand is decomposed and the target product cannot be obtained. On the other hand, when the heating temperature is lower than 100 ° C., the target product is not sufficiently produced.
マイクロ波以外の加熱手段では、均一且つ急速に加熱する制御が非常に難しい場合があり、仮に原料溶液を１００〜５００℃で加熱しても、偏析等によって無機材料が不均一に分散したり、或いは目的とする多孔性金属錯体や無機材料が得られないといったことがあり、目的とする複合体の収率が悪くなる。 With heating means other than microwaves, it may be very difficult to control uniform and rapid heating, and even if the raw material solution is heated at 100 to 500 ° C., the inorganic material is dispersed unevenly due to segregation or the like, Alternatively, the target porous metal complex or inorganic material may not be obtained, and the yield of the target composite is deteriorated.
照射するマイクロ波は、原料溶液を均一に加熱できれば特に限定はないが、例えば３００Ｍ〜３ＴＨｚ程度の周波数のものを使用することができる。また、目的とする複合体や使用する原料にもよるが、通常、１０分〜３時間程度の短時間の加熱により最終目的物を得ることができる。 The microwave to be irradiated is not particularly limited as long as the raw material solution can be heated uniformly. For example, a microwave having a frequency of about 300 M to 3 THz can be used. Moreover, although it depends on the target composite and the raw material to be used, the final target product can usually be obtained by heating in a short time of about 10 minutes to 3 hours.
本願第１発明においては、原料溶液内に多孔性金属錯体と無機材料とが一度に析出するため、多孔性金属錯体内に無機材料が入り込みやすく、それ故、多孔性金属錯体中に無機材料が十分に分散した複合体を得ることができる。 In the first invention of the present application, since the porous metal complex and the inorganic material precipitate at a time in the raw material solution, the inorganic material easily enters the porous metal complex. Therefore, the inorganic material is contained in the porous metal complex. A sufficiently dispersed complex can be obtained.
次に本願第２発明について説明する。 Next, the second invention of the present application will be described.
第２発明においては、上述した第１発明と同様にして原料溶液を調製した後、原料溶液に対して第１の析出処理を行うことにより、先ず多孔性金属錯体を析出させる。 In the second invention, after preparing the raw material solution in the same manner as the first invention described above, the porous metal complex is first precipitated by performing the first precipitation treatment on the raw material solution.
ここで第１の析出処理とは、主に多孔性金属錯体を析出させるために原料溶液に対して行われる処理のことであり、その手段は限定されないが、好ましくは噴霧乾燥である。 Here, the first precipitation treatment is a treatment performed on the raw material solution mainly for precipitating the porous metal complex, and the means thereof is not limited, but is preferably spray drying.
なお、ここで「主に多孔性金属錯体を析出させる」とは原料溶液中に析出した生成物の殆どが多孔性金属錯体であることを意味し、無機材料が全く析出していない状態を要件とするものではない。すなわち、第１の析出処理が終わった段階で僅かに無機材料が析出していても構わない。 Here, “mainly depositing a porous metal complex” means that most of the product precipitated in the raw material solution is a porous metal complex, and the condition that no inorganic material is precipitated is a requirement. It is not something to do. That is, the inorganic material may be slightly deposited at the stage where the first deposition process is completed.
噴霧乾燥の具体例としては、先ず調製した原料溶液を気相中に噴霧し、微細な原料溶液の液滴を生成し、加熱乾燥する。ここで噴霧方法について特に限定はなく、例えば公知の超音波式や二流体ノズル式の噴霧器を使用することができる。液滴は気相中に１０〜１００ｇ／Ｌの濃度になるように噴霧されることが望ましい。 As a specific example of spray drying, first, the prepared raw material solution is sprayed into the gas phase to produce fine raw material solution droplets, which are then heated and dried. Here, the spraying method is not particularly limited, and for example, a known ultrasonic type or two-fluid nozzle type sprayer can be used. It is desirable that the droplets are sprayed in the gas phase so as to have a concentration of 10 to 100 g / L.
そして、気相中に噴霧された原料溶液の液滴を電気炉等の加熱手段により加熱乾燥する。その一例としては、噴霧器によって霧化した原料溶液の液滴を、キャリアガスと共に電気炉中に搬送することによって、当該液滴を加熱する。 And the droplet of the raw material solution sprayed in the gaseous phase is heat-dried by heating means, such as an electric furnace. As an example, the droplets of the raw material solution atomized by the sprayer are transported into the electric furnace together with the carrier gas to heat the droplets.
キャリアガスを使用する場合、その種類には特に制限はなく、空気、酸素、水蒸気等の酸化性ガスや、窒素、アルゴン等の不活性ガス、或いはこれらの混合ガスを使用することができる。 When using carrier gas, there is no restriction | limiting in particular, Oxidizing gas, such as air, oxygen, and water vapor | steam, inert gas, such as nitrogen and argon, or these mixed gas can be used.
加熱温度は目的とする多孔性金属錯体や、使用する原料にもよるが、１００〜５００℃の範囲が好ましい。５００℃を越えると有機配位子が分解してしまい多孔性金属錯体が得られず、１００℃未満では多孔性金属錯体の生成が不十分である。 Although heating temperature is based also on the target porous metal complex and the raw material to be used, the range of 100-500 degreeC is preferable. When the temperature exceeds 500 ° C., the organic ligand is decomposed and a porous metal complex cannot be obtained. When the temperature is lower than 100 ° C., the formation of the porous metal complex is insufficient.
噴霧乾燥における加熱時間に特に限定はなく、目的とする多孔性金属錯体や、使用する原料にもよるが、通常、０．１〜１０秒程度の短時間の加熱で目的の多孔性金属錯体を得ることができる。 There is no particular limitation on the heating time in spray drying, and the target porous metal complex is usually obtained by heating in a short time of about 0.1 to 10 seconds, although it depends on the target porous metal complex and the raw material used. Can be obtained.
以上に説明した噴霧工程並びに加熱工程を実現できる具体的な装置としては、既知のスプレードライヤーや、特公昭６３−３１５２２号公報、特許第３２７７８２３号等に記載されている噴霧熱分解装置を活用することができる。 As a specific apparatus capable of realizing the spraying process and the heating process described above, a known spray dryer or a spray pyrolysis apparatus described in Japanese Patent Publication No. 63-31522, Japanese Patent No. 3277823, or the like is utilized. be able to.
上記の加熱工程の後、気相中に生成した多孔性金属錯体粒子は、必要に応じて冷却等を行った後、サイクロン等の公知の回収手段により回収される。 After the heating step, the porous metal complex particles generated in the gas phase are cooled or the like as necessary, and then collected by a known collecting means such as a cyclone.
上記加熱工程では主に多孔性金属錯体が析出し、無機材料は前駆体の状態のまま多孔性金属錯体粒子の内部に残留しやすい。なお、当該無機材料前駆体としては、先の噴霧乾燥の条件や雰囲気（例えば温度、時間、酸化性キャリアガスの使用の有無、等）に起因して、「無機材料となる化合物が原料溶液から析出した固体状析出物」「当該化合物が酸化等の反応を受けた反応生成物」、更に場合によっては「溶媒の一部が残り、これに溶解した状態の溶液」といった様々な状態・形態であり得るが、そのいずれも含む。 In the heating step, the porous metal complex mainly precipitates, and the inorganic material tends to remain inside the porous metal complex particles in the precursor state. As the inorganic material precursor, “a compound that becomes an inorganic material is derived from a raw material solution due to the previous spray drying conditions and atmosphere (for example, temperature, time, presence / absence of use of an oxidizing carrier gas, etc.). In various states and forms, such as “a solid precipitate that has been deposited”, “a reaction product in which the compound has undergone a reaction such as oxidation”, and in some cases “a solution in which a part of the solvent remains and is dissolved therein”. Possible, but any of them.
そこで本願第２発明では、回収した多孔性金属錯体粒子に対して第２の析出処理を行う。 Therefore, in the second invention of the present application, a second precipitation treatment is performed on the recovered porous metal complex particles.
第２の析出処理は、多孔性金属錯体粒子内に含まれている無機材料の前駆体から無機材料を析出させることができれば良く、限定されるものではないが、その一例としては加熱処理や酸化処理、還元処理等が挙げられる。なお、この際、既に生成した多孔性金属錯体を分解や溶解、汚損等の影響がないよう、雰囲気や諸条件等が設定されることは勿論である。 The second precipitation treatment is not limited as long as the inorganic material can be precipitated from the precursor of the inorganic material contained in the porous metal complex particles, and examples thereof include heat treatment and oxidation. Treatment, reduction treatment and the like. In this case, it is needless to say that the atmosphere, various conditions, and the like are set so that the porous metal complex that has already been generated is not affected by decomposition, dissolution, fouling, or the like.
加熱処理の場合、多孔性金属錯体粒子内に含まれる無機材料の前駆体にも依存するが加熱温度８０〜５００℃で３０分から３時間程度の加熱が好ましい。 In the case of heat treatment, although it depends on the precursor of the inorganic material contained in the porous metal complex particles, heating at a heating temperature of 80 to 500 ° C. for about 30 minutes to 3 hours is preferable.
以下、更に本願第３発明について説明する。第３発明は、多孔性金属錯体と無機材料を析出させる前に、目的物である複合体の前駆体粒子を生成する工程を備える。 The third invention of the present application will be further described below. The third invention includes a step of generating precursor particles of a composite which is a target product before depositing a porous metal complex and an inorganic material.
一例を挙げると、例えば、前述の第１の析出処理のため、原料溶液に対して噴霧乾燥を行った時に、多孔性金属錯体も無機材料も析出せず、多孔性金属錯体の前駆体と無機材料の前駆体を含む、複合体の前駆体粒子が析出することがある。これは、原料溶液として、水系溶媒を用いて調製した原料水溶液を使用した場合に特に顕著である。 As an example, for example, when the raw material solution is spray-dried for the first precipitation treatment described above, neither the porous metal complex nor the inorganic material is precipitated, and the precursor of the porous metal complex and the inorganic Composite precursor particles, including material precursors, may precipitate out. This is particularly remarkable when a raw material aqueous solution prepared using an aqueous solvent is used as the raw material solution.
この前駆体粒子中には多孔性金属錯体の前駆体に無機材料前駆体が分散して含まれていることから、この前駆体粒子に対して更に、第１発明と同様の、多孔性金属錯体と無機材料が一度に析出する析出処理を行うか、或いは第２発明と同様の、多孔性金属錯体を析出させた後に無機材料を析出させる二段階の析出処理を行うことにより、本発明が目的とする、多孔性金属錯体内に無機材料が分散した複合体を得ることができる。ここでは複合体の前駆体粒子を析出させる処理をプレ析出処理と言い、多孔性金属錯体と無機材料を一度に又は二段階に分けて析出させる処理を総称して本析出処理と言う。 In this precursor particle, since the inorganic material precursor is dispersed and contained in the precursor of the porous metal complex, the same porous metal complex as in the first invention is further added to the precursor particle. Or the inorganic material is deposited at the same time, or the same two-stage precipitation treatment as that of the second invention, in which the inorganic material is deposited after the porous metal complex is deposited. A composite in which an inorganic material is dispersed in a porous metal complex can be obtained. Here, the treatment for precipitating the precursor particles of the composite is referred to as pre-deposition treatment, and the treatment for precipitating the porous metal complex and the inorganic material in one step or in two stages is collectively referred to as the main precipitation treatment.
すなわち本析出処理の一例としては、析出した複合体の前駆体粒子に対し、マイクロ波等による加熱を行って多孔性金属錯体と無機材料とを一度に析出させても良く、或いは、先ず加熱乾燥して多孔性金属錯体粒子を析出させた後、その内部に含まれている無機材料の前駆体から無機材料を析出させるための加熱処理や酸化処理、還元処理等を行っても良い。 That is, as an example of the present precipitation treatment, the deposited composite precursor particles may be heated by microwaves or the like to precipitate the porous metal complex and the inorganic material at one time, or first heated and dried. Then, after depositing the porous metal complex particles, a heat treatment, an oxidation treatment, a reduction treatment or the like for precipitating the inorganic material from the precursor of the inorganic material contained therein may be performed.
以下では、一般的或いは代表的な多孔性金属錯体である［Ｚｎ（２ＭｅＩＭ）２］（以下、ＺＩＦ−８と称する）と複数種の無機材料との複合体を製造した例を説明するが、本発明はこれに限られるものではなく、勿論、他の多孔性金属錯体を用いた複合体を製造することができる。 Hereinafter, an example in which a composite of [Zn (2MeIM) 2 ] (hereinafter referred to as ZIF-8), which is a general or representative porous metal complex, and a plurality of types of inorganic materials will be described. The present invention is not limited to this, and of course, composites using other porous metal complexes can be produced.
〔実施例１〕
酢酸亜鉛・二水和物０．２２４ｇ（１．０ｍモル）及び２−メチルイミダゾール０．１６４ｇ（２．０ｍモル）をそれぞれ溶媒であるジメチルホルムアミド１０ｍｌに完全に溶解させ、さらにその２−メチルイミダゾールの溶液に酢酸パラジウム０．０３１ｇ（０．１４ｍモル）を加えて完全に溶解させ、液温を２５℃に保ったまま攪拌することによって原料溶液を調製した。
[Example 1]
Zinc acetate dihydrate 0.224 g (1.0 mmol) and 2-methylimidazole 0.164 g (2.0 mmol) were completely dissolved in 10 ml of dimethylformamide as a solvent, respectively, and the 2-methylimidazole was further dissolved. To this solution, 0.031 g (0.14 mmol) of palladium acetate was added and completely dissolved, and the raw material solution was prepared by stirring while keeping the liquid temperature at 25 ° C.
上記原料溶液２０ｍｌをバイアルに入れ、マイクロ波を照射し、反応温度１４０℃で１時間の加熱処理を行った。 20 ml of the raw material solution was placed in a vial, irradiated with microwaves, and heat-treated at a reaction temperature of 140 ° C. for 1 hour.
上記加熱処理後、遠心分離にて沈殿物を回収した後に、アルコールで洗浄して、室温で真空乾燥を行って、０．１７ｇの粉末状生成物を得た。 After the heat treatment, the precipitate was collected by centrifugation, washed with alcohol, and vacuum dried at room temperature to obtain 0.17 g of a powdery product.
この粉末状生成物に対して以下の分析を行った。 The following analysis was performed on this powdery product.
先ず、リガク製全自動Ｘ線回折装置ＲＩＮＴ ＵＬＴＩＭＡ ＩＩを用いてＸＲＤ測定を行うと共に、日本分光製フーリエ変換赤外分光分析装置ＦＴ／ＩＲ−６２００を用いてＦＴ−ＩＲ測定を行った。なお、ここでＦＴ−ＩＲはＡＴＲ法で測定した。各測定結果をそれぞれ図１、図２に示す。 First, XRD measurement was performed using a fully automatic X-ray diffractometer RINT ULTIMA II manufactured by Rigaku, and FT-IR measurement was performed using a Fourier transform infrared spectroscopic analyzer FT / IR-6200 manufactured by JASCO Corporation. Here, FT-IR was measured by the ATR method. The measurement results are shown in FIGS. 1 and 2, respectively.
図１、図２より、得られた粉末状生成物中に、ＺＩＦ−８と金属Ｐｄの存在を確認できた。 1 and 2, the presence of ZIF-8 and metal Pd could be confirmed in the obtained powdery product.
次に、日本電子製電界放出形走査電子顕微鏡ＪＳＭ−７０００Ｆを用いてＳＥＭ像を観察すると共に、日立透過電子顕微鏡Ｈ−９５００を用いてＴＥＭ像を観察した。その結果をそれぞれ図３、図４に示す。 Next, an SEM image was observed using a JEM field emission scanning electron microscope JSM-7000F, and a TEM image was observed using a Hitachi transmission electron microscope H-9500. The results are shown in FIGS. 3 and 4, respectively.
図３、図４より、得られた粉末状生成物は、約２０〜３０ｎｍの粒径の一次粒子が凝集した約０．２〜０．３μｍの二次粒子であり、図１、図２の結果と合わせて、当該粉末状生成物が、ＺＩＦ−８内に金属Ｐｄが分散した複合体であることを確認することができた。 From FIG. 3 and FIG. 4, the obtained powdery product is a secondary particle of about 0.2 to 0.3 μm in which primary particles of a particle size of about 20 to 30 nm are aggregated. Together with the results, it was confirmed that the powdered product was a composite in which metal Pd was dispersed in ZIF-8.
〔実施例２〕
酢酸パラジウムをアセチルアセトナト銅０．０６０ｇ（０．２３ｍモル）に変更した以外は実施例１と同様にして原料溶液を調製した後、実施例１と同様にマイクロ波を照射することによって粉末状生成物を得た。
[Example 2]
A raw material solution was prepared in the same manner as in Example 1 except that palladium acetate was changed to 0.060 g (0.23 mmol) of acetylacetonatocopper, and then powdered by irradiation with microwaves in the same manner as in Example 1. The product was obtained.
得られた粉末状生成物０．１３ｇに対し、実施例１と同様に、ＸＲＤ測定、ＦＴ−ＩＲ測定、ＳＥＭ像観察、ＴＥＭ像観察を行った。それらの結果をそれぞれ図５〜図８に示す。 XRD measurement, FT-IR measurement, SEM image observation, and TEM image observation were performed on 0.13 g of the obtained powdery product in the same manner as in Example 1. The results are shown in FIGS.
図５〜図８の結果より、当該粉末状生成物が、ＺＩＦ−８内に金属Ｃｕが分散した複合体であることを確認することができた。 From the results of FIGS. 5 to 8, it was confirmed that the powdery product was a composite in which metal Cu was dispersed in ZIF-8.
〔実施例３〕
実施例１と同様に調製した原料溶液を、流体ノズルを用いて霧化しながら２５０℃に設定した加熱炉に送り込んだ。この際、キャリアガスとして窒素ガスを用い、ガス流量は０．５Ｌ／ｍｉｎとして加熱炉内での加熱時間が２〜３秒になるよう制御した。
Example 3
The raw material solution prepared in the same manner as in Example 1 was fed into a heating furnace set at 250 ° C. while being atomized using a fluid nozzle. At this time, nitrogen gas was used as the carrier gas, the gas flow rate was set to 0.5 L / min, and the heating time in the heating furnace was controlled to be 2 to 3 seconds.
加熱炉の出口にサイクロン捕集器を取り付けて、加熱炉で生成された粉末を回収し、真空乾燥処理を行うことにより、ほぼ白色の粉末状生成物を得た。但し、この白色の粉末状生成物についてＸＲＤ測定を行ったが金属Ｐｄの存在は確認できなかった。 A cyclone collector was attached to the outlet of the heating furnace, the powder generated in the heating furnace was collected, and vacuum drying was performed to obtain a substantially white powdery product. However, XRD measurement was performed on this white powdery product, but the presence of metal Pd could not be confirmed.
次に上記白色の粉末状生成物０．１０ｇを、管状炉を用いて嫌気下２５０℃、６０分間の加熱処理を行うことにより、灰色の粉末状生成物が得られた。実施例１と同様に、この灰色の粉末状生成物０．０９ｇに対してＸＲＤ測定、ＦＴ−ＩＲ測定、ＳＥＭ像観察、ＴＥＭ像観察を行った。それらの結果をそれぞれ図９〜図１２に示す。 Next, 0.10 g of the white powdery product was subjected to heat treatment at 250 ° C. for 60 minutes under anaerobic conditions using a tubular furnace, to obtain a gray powdery product. In the same manner as in Example 1, 0.09 g of this gray powdery product was subjected to XRD measurement, FT-IR measurement, SEM image observation, and TEM image observation. The results are shown in FIGS.
図９〜図１２より、当該灰色の粉末状生成物が、ＺＩＦ−８内に金属Ｐｄが分散した複合体であることを確認することができた。 9 to 12, it was confirmed that the gray powdery product was a composite in which metal Pd was dispersed in ZIF-8.
〔実施例４〕
酢酸パラジウムを酢酸銀０．０４８ｇ（０．２８ｍモル）に変更した以外は実施例１と同様に原料溶液を調製した後、実施例３と同様に噴霧乾燥処理と加熱処理を行って粉末状生成物０．１５ｇを得た。
Example 4
A raw material solution was prepared in the same manner as in Example 1 except that palladium acetate was changed to 0.048 g (0.28 mmol) of silver acetate, and then spray-dried and heated in the same manner as in Example 3 to form a powder. 0.15 g of product was obtained.
同様にＸＲＤ測定、ＦＴ−ＩＲ測定、ＳＥＭ像観察、ＴＥＭ像観察を行った結果を図１３〜図１６に示す。 Similarly, the results of XRD measurement, FT-IR measurement, SEM image observation, and TEM image observation are shown in FIGS.
図１３〜図１６より、当該粉末状生成物が、ＺＩＦ−８内に金属Ａｇが分散した複合体であることを確認することができた。 From FIG. 13 to FIG. 16, it was confirmed that the powdered product was a composite in which metal Ag was dispersed in ZIF-8.
〔実施例５〕
酢酸パラジウムをアセチルアセトナトパラジウム０．０４３ｇ（０．１４ｍモル）に変更した以外は実施例１と同様に原料溶液を調製した後、実施例３と同様に噴霧乾燥処理と加熱処理を行って粉末状生成物０．１７ｇを得た。
Example 5
A raw material solution was prepared in the same manner as in Example 1 except that palladium acetate was changed to 0.043 g (0.14 mmol) of acetylacetonatopalladium, followed by spray drying and heating in the same manner as in Example 3. 0.17 g of a product was obtained.
同様にＸＲＤ測定、ＦＴ−ＩＲ測定、ＳＥＭ像観察、ＴＥＭ像観察を行ったところ実施例３とほぼ同様の結果であり、当該粉末状生成物が、ＺＩＦ−８内に金属Ｐｄが分散した複合体であることを確認することができた。 Similarly, when XRD measurement, FT-IR measurement, SEM image observation, and TEM image observation were performed, the results were almost the same as in Example 3. The powdered product was a composite in which metal Pd was dispersed in ZIF-8. I was able to confirm that it was a body.
〔実施例６〕
酢酸亜鉛・二水和物の添加量を０．６７２ｇ（３．０ｍモル）に増量した以外は実施例１と同様に原料溶液を調製した後、実施例３と同様に噴霧乾燥処理と加熱処理を行って粉末状生成物０．１５ｇを得た。
Example 6
A raw material solution was prepared in the same manner as in Example 1 except that the amount of zinc acetate dihydrate added was increased to 0.672 g (3.0 mmol), and then spray drying treatment and heat treatment were conducted in the same manner as in Example 3. To obtain 0.15 g of a powdery product.
同様にしてＸＲＤ測定、ＦＴ−ＩＲ測定、ＳＥＭ像観察、ＴＥＭ像観察を行い、当該粉末状生成物が、ＺＩＦ−８内に金属ＰｄとＺｎＯが分散した複合体であることを確認することができた。 Similarly, XRD measurement, FT-IR measurement, SEM image observation, and TEM image observation are performed to confirm that the powdery product is a composite in which metal Pd and ZnO are dispersed in ZIF-8. did it.
〔実施例７〕
酢酸亜鉛・二水和物０．４３９ｇ（２．０ｍモル）及び２−メチルイミダゾール１．３１ｇ（１６ｍモル）をそれぞれ溶媒である水５０ｍｌに完全に溶解させ、液温を２５℃に保ったまま１５分間攪拌した。その後、酢酸銅・一水和物０．０９４ｇ（０．４７ｍモル）を水５ｍｌに溶解した水溶液を添加しさらに１５分撹拌することで原料溶液を得た。
Example 7
Zinc acetate dihydrate 0.439 g (2.0 mmol) and 2-methylimidazole 1.31 g (16 mmol) were completely dissolved in 50 ml of water as a solvent, respectively, and the liquid temperature was kept at 25 ° C. Stir for 15 minutes. Thereafter, an aqueous solution in which 0.094 g (0.47 mmol) of copper acetate monohydrate was dissolved in 5 ml of water was added and further stirred for 15 minutes to obtain a raw material solution.
この原料溶液を、２流体ノズルを用いて霧化し、２２０℃に加熱した空気と混合して水を蒸発させることにより、粉末状の前駆体化合物を合成した。生成した前駆体化合物はサイクロン捕集器で回収した。 This raw material solution was atomized using a two-fluid nozzle, mixed with air heated to 220 ° C., and water was evaporated to synthesize a powdery precursor compound. The produced precursor compound was recovered with a cyclone collector.
この前駆体化合物に対し、ＸＲＤ測定、ＦＴ−ＩＲ測定を行った結果を、図１７〜１８に示す。これらの図から明らかなように、前駆体化合物においてはＺＩＦ−８の回折パターンも金属Ｃｕのピークも観測されず、Ｘ線的には非晶質であった。 The result of having performed XRD measurement and FT-IR measurement with respect to this precursor compound is shown to FIGS. As is clear from these figures, in the precursor compound, neither the diffraction pattern of ZIF-8 nor the peak of metallic Cu was observed, and it was amorphous in X-ray.
続いて、この前駆体化合物に対し、１５０℃で減圧乾燥処理を行ったところ、０．６０ｇの粉末状の生成物（以下、乾燥粉末と称する）が得られた。この乾燥粉末に対して、同様にＸＲＤ測定、ＦＴ−ＩＲ測定を行った結果を図１７〜１８に併記する。これらの図から示される通り、上記乾燥処理を行った後には、ＺＩＦ−８由来と考えられる回折パターンが見られるようになったが、金属Ｃｕのピークは未だ観察されなかった。 Subsequently, when this precursor compound was dried under reduced pressure at 150 ° C., 0.60 g of a powdery product (hereinafter referred to as dry powder) was obtained. The results of XRD measurement and FT-IR measurement performed on this dry powder are also shown in FIGS. As shown in these figures, after performing the above drying treatment, a diffraction pattern considered to be derived from ZIF-8 came to be seen, but the peak of metal Cu was not yet observed.
更に、乾燥粉末０．３０ｇを管状炉内に静置し、水素を４％含む窒素ガス中で４００℃で６０分の熱処理を行ったところ、褐色の粉末状生成物０．２５ｇが得られた。このときのＸＲＤ測定、ＦＴ−ＩＲ測定の結果を図１７〜１８に併記した。図から示される通り、ＺＩＦ−８の結晶化が進み、金属Ｃｕもそのピークが出現するようになった。 Further, 0.30 g of the dry powder was allowed to stand in a tubular furnace and subjected to a heat treatment at 400 ° C. for 60 minutes in a nitrogen gas containing 4% of hydrogen. . The results of XRD measurement and FT-IR measurement at this time are also shown in FIGS. As shown in the figure, the crystallization of ZIF-8 has progressed, and the peak of metal Cu also appears.
この褐色の粉末状生成物に対して、図１９にＳＥＭ像観察した結果を、またＦＥＩ製ＴＩＴＡＮ８０−３００による明視野ＴＥＭ像観察した結果を図２０に示す。図１９に示されるように、ここで得られた粉末状生成物はミクロンオーダーの粒子であり、図２０から当該粒子が内部にＺＩＦ−８の一次粒子の集合体を含み、特に粒子界面の近傍に多数のＣｕ微粒子が分散した複合体であることを確認することができた。 FIG. 19 shows the result of SEM image observation of this brown powder product, and FIG. 20 shows the result of bright field TEM image observation by FEI TITAN 80-300. As shown in FIG. 19, the powdered product obtained here is a micron order particle, and from FIG. 20, the particle contains an aggregate of primary particles of ZIF-8 inside, particularly in the vicinity of the particle interface. It was confirmed that the composite was dispersed with a large number of Cu fine particles.
更に、得られた粉末状生成物に対し、日本ベル製自動比表面積/細孔分布測定器ＢＥＬＳＯＲＰ−ｍｉｎｉ IIを用い、ＣＯ２を測定ガスとして１９５ＫでＣＯ２ガス吸着能を測定した結果を図２１に記す。この結果から、得られた粉末状生成物が空孔を有することを確認できた。 Furthermore, for the obtained powdery product, the results of measuring the CO 2 gas adsorption capacity at 195 K using CO 2 as the measurement gas using an automatic specific surface area / pore distribution measuring device BELSORP-mini II manufactured by Bell Japan 21. From this result, it was confirmed that the obtained powdery product had pores.
〔実施例８〕
酢酸銅・一水和物の代わりにトリスアセチルアセトナトルテニウム〔Ｒｕ（Ｃ５Ｈ７Ｏ２）３〕 ０．１２ｇ（０．３０ｍモル）をエタノール２０ｍｌに溶解し混合した以外は実施例７と同様に行った結果、ＺＩＦ−８の一次粒子と金属Ｒｕ微粒子からなる複合体であることを確認することができた。
Example 8
Example 7 except that 0.12 g (0.30 mmol) of trisacetylacetonatoruthenium [Ru (C 5 H 7 O 2 ) 3 ] was dissolved and mixed in 20 ml of ethanol instead of copper acetate monohydrate. As a result of the same operation, it was confirmed that the composite was composed of primary particles of ZIF-8 and metal Ru fine particles.
Claims (6)
前記中心金属を含む化合物、前記有機配位子となる化合物、及び、前記無機材料となる化合物が溶解している原料溶液を調製する調製処理と、
前記原料溶液に対してマイクロ波の照射による加熱を行って前記原料溶液から前記多孔性金属錯体と前記無機材料を一度に析出させる析出処理を行うことにより、
前記多孔性金属錯体に前記無機材料が内包された複合体を生成することを特徴とする製造方法。 A porous metal complex having a porous structure formed by accumulating a central metal and an organic metal complex containing an organic ligand coordinated to the central metal, and an inorganic material encapsulated in the porous metal complex A method for producing a composite comprising:
A preparation process for preparing a raw material solution in which the compound including the central metal, the compound serving as the organic ligand, and the compound serving as the inorganic material are dissolved;
By subjecting the raw material solution to heating by microwave irradiation to perform precipitation treatment for precipitating the porous metal complex and the inorganic material at a time from the raw material solution,
A method for producing a composite in which the inorganic material is encapsulated in the porous metal complex.
前記中心金属を含む化合物、前記有機配位子となる化合物、及び、前記無機材料となる化合物が溶解している原料溶液を調製する調製工程と、
前記原料溶液を噴霧乾燥することにより前記原料溶液から前記多孔性金属錯体を析出させる第１の析出処理と、
前記第１の析出処理を行った後、加熱処理、酸化処理、還元処理の何れかを行って前記無機材料を析出させる第２の析出処理を行うことにより、
前記多孔性金属錯体に前記無機材料が内包された複合体を生成することを特徴とする製造方法。 A porous metal complex having a porous structure formed by integrating an organic metal complex including a central metal and an organic ligand coordinated to the central metal, and an inorganic material included in the porous metal complex A method for producing a composite comprising:
A preparation step of preparing a raw material solution in which the compound containing the central metal, the compound serving as the organic ligand, and the compound serving as the inorganic material are dissolved;
A first precipitation treatment for precipitating the porous metal complex from the raw material solution by spray drying the raw material solution;
After performing the first precipitation treatment, by performing a second precipitation treatment for depositing the inorganic material by performing any of heat treatment, oxidation treatment, reduction treatment ,
A method for producing a composite in which the inorganic material is encapsulated in the porous metal complex.
前記中心金属を含む化合物、前記有機配位子となる化合物、及び、前記無機材料となる化合物が溶解している原料溶液を調製する調製工程と、
前記原料溶液を噴霧乾燥することにより前記原料溶液から前記複合体の前駆体粒子を析出させるプレ析出処理と、
前記プレ析出処理を行った後、前記複合体の前駆体粒子に対してマイクロ波の照射による加熱を行って多孔性金属錯体と無機材料とを一度に析出させることにより、或いは、前記複合体の前駆体粒子を加熱乾燥処理により多孔性金属錯体粒子を析出させた後、その内部に含まれている無機材料の前駆体から無機材料を析出させるための加熱処理、酸化処理、還元処理の何れかを行うことにより、前記多孔性金属錯体と前記無機材料を析出させる本析出処理を行うことにより、
前記多孔性金属錯体に前記無機材料が内包された複合体を生成することを特徴とする製造方法。 A porous metal complex having a porous structure formed by integrating an organic metal complex including a central metal and an organic ligand coordinated to the central metal, and an inorganic material included in the porous metal complex A method for producing a composite comprising:
A preparation step of preparing a raw material solution in which the compound containing the central metal, the compound serving as the organic ligand, and the compound serving as the inorganic material are dissolved;
Pre-precipitation treatment for precipitating the precursor particles of the composite from the raw material solution by spray drying the raw material solution;
After performing the pre-deposition treatment, the precursor particles of the composite are heated by microwave irradiation to precipitate the porous metal complex and the inorganic material at one time, or After precipitating porous metal complex particles by heat drying treatment of precursor particles, any of heat treatment, oxidation treatment, reduction treatment for precipitating inorganic material from the precursor of inorganic material contained therein By carrying out the present precipitation treatment for precipitating the porous metal complex and the inorganic material,
A method for producing a composite in which the inorganic material is encapsulated in the porous metal complex.
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