CN1656104A - 包含金属-有机骨架材料的成形体 - Google Patents
包含金属-有机骨架材料的成形体 Download PDFInfo
- Publication number
- CN1656104A CN1656104A CNA038125196A CN03812519A CN1656104A CN 1656104 A CN1656104 A CN 1656104A CN A038125196 A CNA038125196 A CN A038125196A CN 03812519 A CN03812519 A CN 03812519A CN 1656104 A CN1656104 A CN 1656104A
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- Prior art keywords
- metal
- molding
- organic framework
- framework materials
- dmf
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 103
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 38
- -1 aluminum compound Chemical class 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
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- 238000006703 hydration reaction Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
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- 238000007598 dipping method Methods 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
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- 238000001764 infiltration Methods 0.000 claims description 2
- 150000001455 metallic ions Chemical class 0.000 claims description 2
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- 239000002002 slurry Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
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- 239000011701 zinc Substances 0.000 description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 30
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 15
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- 238000002360 preparation method Methods 0.000 description 13
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
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- 239000002904 solvent Substances 0.000 description 10
- 239000013132 MOF-5 Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- IYSNYCQLARBERC-UHFFFAOYSA-N methylsulfinylmethane;toluene Chemical compound CS(C)=O.CC1=CC=CC=C1 IYSNYCQLARBERC-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
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- 229910052726 zirconium Inorganic materials 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 101100353526 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pca-2 gene Proteins 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
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- 239000012298 atmosphere Substances 0.000 description 2
- LMAQRGNIWKAAFR-UHFFFAOYSA-N benzene;dicarboxy carbonate Chemical compound C1=CC=CC=C1.OC(=O)OC(=O)OC(O)=O LMAQRGNIWKAAFR-UHFFFAOYSA-N 0.000 description 2
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- 230000000536 complexating effect Effects 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KGIIQLWZRGRVOY-UHFFFAOYSA-N ethanol;1,4-xylene Chemical compound CCO.CC1=CC=C(C)C=C1 KGIIQLWZRGRVOY-UHFFFAOYSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
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- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- NWKYZYGOSPOKDY-UHFFFAOYSA-N n,n-dimethylformamide;pyridine Chemical compound CN(C)C=O.C1=CC=NC=C1 NWKYZYGOSPOKDY-UHFFFAOYSA-N 0.000 description 1
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种包含金属-有机骨架的新型成形体。所述金属-有机骨架材料含有至少一种金属离子和至少一种至少双配位的有机化合物及至少一种微孔和中孔或者微孔或中孔。所述成形体含有至少一种金属-有机骨架材料,并可选择包含其它物质,特别是至少一种载体。
Description
本发明涉及一种包含金属-有机骨架材料的新型成形体。所述金属-有机骨架材料含有至少一种金属离子和至少一种至少双配位的有机化合物并具有至少一种微孔和中孔或者微孔或中孔。所述成形体含有至少一种金属-有机骨架材料,并可选择包含其它物质,特别是至少一种载体。
在诸多材料中,具有大的内表面积(优选是由孔或孔道限定的)的材料对于分析中的运用、吸收和/或吸附技术、离子交换、色谱法、贮存和/或摄取物质是特别有利的。根据现有技术制备固体多孔材料在例如Gerhard Ertl,Helmut Knzinger,Jens Weitkamp(Eds.),Wiley VCH,WeinHeim,1999的《固体催化剂的制备》(Preparation of Solid Catalysts)中有描述。其中,固体多孔材料是通过沉淀、溶胶-凝胶、喷雾干燥、发泡等方法制备的。
在制备微孔和/中孔活性材料的具有前景的新颖替代合成方案中,使用金属离子和分子有机结构单元生成所谓的金属-有机骨架(MOFs)。这种金属-有机骨架材料在例如US 5,648,508、EP-A-0 709 253、M.O’Keeffe等人的J.Sol.State Chem.,
152(2000)p.3-20、H.Li等人的Nature
402(1999)p.276以下、M.Eddaoudi等人的Topics in Catalysis
9(1999)p.105-111、B.Chen等人的Science
291(2001)p.1021-23中有描述。这些新颖材料的优点、特别是在分析运用中的优点如下:(i)可以获得的孔尺寸比目前使用的沸石中的更大,(ii)内表面积比目前使用的多孔材料的更大,(iii)可以制得宽范围的孔尺寸和/或孔道结构,(iv)可容易地对形成内表面的有机骨架组分进行官能化。
但是这种基于金属-有机骨架的新颖多孔材料通常只能获得小微晶或粉末的形式,并且这种形式的多孔材料不能用于需要成形体的场合。
因此,本发明的一个目标是提供具有包含金属-有机骨架的材料的特性的成形体。本发明中使用的术语“成形体”是指通过成型工艺获得的成形体以及将活性材料施用到(多孔)基体上而获得的成形体。术语“成形体”将在下文中进一步定义。
这一目标可通过使至少一种包含金属-有机骨架的材料经过成型步骤、或将所述材料施用于基底上、或进行这两种操作的组合而达到。这种金属-有机骨架含有孔、至少一种金属离子和至少一种至少双配位的有机化合物,该有机化合物配位键联到所述金属离子上。因此,本发明涉及:一种金属-有机骨架材料,其含有孔、至少一种金属离子和至少一种至少双配位的有机化合物,该有机化合物配位键联到所述金属离子上。该金属-有机骨架材料的特征在于它是以成形体形式存在的。本发明还涉及一种制造如上所述以成形体形式存在的金属-有机骨架材料的方法,其特征在于成形体是通过至少一个成型步骤而获得的。本发明还涉及一种制造如上所述以成形体形式存在的金属-有机骨架材料的方法,其特征在于成形体是通过使至少一种金属-有机骨架材料与至少一种基体接触而获得的。本发明还涉及如上所述的骨架材料的用途,用作催化剂、催化剂载体、吸附作用载体、液体存储载体、干燥剂、离子交换材料、分子筛(分离器)、用于色谱法的材料、用于选择性释放和/或摄取分子的材料、分子识别、纳米管、纳米反应器。
如上所述,金属-有机骨架材料在例如US 5,648,508、EP-A-0 709 253、M.O’Keeffe等人的J.Sol.State Chem.,
152(2000)p.3-20、H.Li等人的Nature
402(1999)p.276以下、M.Eddaoudi等人的Topics in Catalysis
9(1999)p.105-111、B.Chen等人的Science
291(2001)p.1021-23中有所描述。所述材料的廉价制备方法是DE 10111230.0的主题。上述文献的内容,此处作为参考,全部结合进本发明的内容。
金属-有机骨架材料(如本发明中所用的)包含孔,特别是微孔和/或中孔。按照Pure Applied Chem.
45,p.71以下尤其是p.79(1976)给出的定义,微孔定义为直径为2nm或2nm以下的孔,中孔为直径为2nm至50nm范围内的孔。微孔和/或中孔的存在,可通过按照DIN 66131和/或DIN66134测定金属-有机骨架材料在77K下摄取氮气的能力的吸附测量进行监测。
例如,I-型等温曲线表明存在微孔[例如参阅M.Eddaoudi等人的Topics in Catalysis
9(1999)第4段]。在一个优选实施方案中,按照朗缪尔模型(DIN 66131、66134)计算的比表面积优选大于5m2/g,更优选大于10m2/g,更加优选大于50m2/g,尤其优选大于500m2/g,并且可以增加大到大于3000m2/g的区域。
关于根据本发明所采用的骨架材料中的金属组分,尤其要提到的是元素周期表中主族元素和副族元素中的金属离子,即Ia、IIa、IIIa、IVa到VIIIa和Ib到VIb族元素的金属离子。在那些金属组分中,特别要提到的是Mg、Ca、Sr、Ba、Sc、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Si、Ge、Sn、Pb、As、Sb和Bi,更优选Zn、Cu、Ni、Pd、Pt、Ru、Rh和Co。关于这些元素的金属离子,尤其要提到的是:Mg2+、Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ti4+、Zr4+、Hf4+、V4+、V3+、V2+、Nb3+、Ta3+、Cr3+、Mo3+、W3+、Mn3+、Mn2+、Re3+、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Hg2+、Al3+、Ga3+、In3+、Tl3+、Si4+、Si2+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、As5+、As3+、As+、Sb5+、Sb3+、Sb+和Bi5+、Bi3+和Bi+。
关于优选的金属离子及其进一步的细节,特别要指出的是:EP-A 0 790253,尤其是p.10,1.8-30,“金属离子”部分,这里引入该部分作为参考。
除EP-A 0 790 253和US 5 648 508公开的金属盐之外,还可使用其它金属化合物,例如硫酸盐、磷酸盐和元素周期表中主族金属和副族金属的其它络合反离子金属盐。优选金属氧化物、混合氧化物、金属氧化物的混合物和/或具有或不具有限定化学计量的混合氧化物。所有上述金属化合物可以是可溶的或不可溶的,并且它们可以以粉末、成形体或其任意组合的形式用作原料。
关于能与金属离子配位的至少双配位的有机化合物,原则上可以使用所有适于该目的并满足上述为至少双配位这一要求的化合物。所述有机化合物必须有至少两个能与金属盐的金属离子、特别是与前述族的金属配位的中心。关于至少双配位的有机化合物,特别要提到的是具有以下结构的化合物:
i)烷基亚结构,具有1至10个碳原子,
ii)芳基亚结构,具有1至5个苯环,
iii)烷基或芳基胺亚结构,由具有1至10个碳原子的烷基或具有1至5个苯环的芳基组成,
所述亚结构键合有至少一种至少双配位的官能团“X”,该官能团与所述化合物的亚结构共价键合,并且其中X选自由CO2H、CS2H、NO2、SO3H、Si(OH)3、Ge(OH)3、Sn(OH)3、Si(SH)4、Ge(SH)4、Sn(SH)3、PO3H、AsO3H、AsO4H、P(SH)3、As(SH)3、CH(RSH)2、C(RSH)3、CH(RNH2)2、C(RNH2)3、CH(ROH)2、C(ROH)3、CH(RCN)2、C(RCN)3,其中R是具有1至5个碳原子的烷基,或是由1至2个苯环组成的芳基,以及CH(SH)2、C(SH)3、CH(NH2)2、C(NH2)2、CH(OH)2、C(OH)3、CH(CN)2和C(CN)3组成的组。
特别要提到的是取代的或未取代的、单环或多环的芳香二、三和四元羧酸,以及取代或未取代的、芳香族的、包含至少一个杂原子的、具有一个或多个环的芳香二、三和四元羧酸。
优选的配体是1,3,5-苯三羧酸(BCT)。其它优选的配位体有ADC(乙炔二羧酸酯/盐)、NDC(萘二羧酸酯/盐)、BDC(苯二羧酸酯/盐)、ATC(金刚烷四羧酸酯/盐)、BTC(苯三羧酸酯/盐)、BTB(三苯甲酸苯酯/盐)、MTB(四苯甲酸甲酯/盐)、ATB(三苯甲酸金刚酯/盐)。
除了至少双配位的有机化合物之外,依据本发明所用的骨架材料还可以含有一种或多种单配位的配体,其优选选自下列单配位的物质和/或其衍生物:
a.烷基胺及其相应的烷基铵盐,其含有具有1至20个碳原子的直链、支链或环状的脂肪族基团(及其相应的铵盐);
b.芳基胺及其相应的芳基铵盐,具有1至5个苯环;
c.烷基鏻盐,含有直链、支链或环状的脂肪族基团,具有1至20个碳原子;
d.芳基鏻盐,具有1至5个苯环;
e.烷基有机酸和相应的烷基有机阴离子(和盐),含有直链、支链或环状的脂肪族基团,具有1至20个碳原子;
f.芳基有机酸及其相应的芳基有机阴离子及盐,具有1至5个苯环;
g.脂肪醇,含有直链、支链或环状的脂肪族基团,具有1至20个碳原子;
h.芳基醇,具有1至5个苯环;
i.无机阴离子,选自由:
硫酸根、硝酸根、亚硝酸根、亚硫酸根、亚硫酸氢根、磷酸根、磷酸氢根、磷酸二氢根、二磷酸根、三磷酸根、亚磷酸根、氯化物、氯酸根、溴化物、溴酸根、碘化物、碘酸根、碳酸根、碳酸氢根,以及上述无机阴离子相应的酸和盐组成的组;
j.氨、二氧化碳、甲烷、氧、乙烯、己烷、苯、甲苯、二甲苯、氯苯、硝基苯、萘、噻吩、吡啶、丙酮、1-2-二氯乙烷、二氯甲烷、四氢呋喃、乙醇胺、三乙胺和三氟甲磺酸。
关于至少双配位的有机化合物和单配位物质(本申请所采用骨架材料的配体由其衍生)的进一步的细节,可以参见EP-A 0 790 253,其相应内容引入本申请作为参考。
在本申请中,含有Zn2+作金属离子、衍生自对苯二甲酸的配位体作双配位化合物的如上所述的骨架材料是特别优选的。在文献中,所述骨架材料为据文献已知的MOF-5。
分别用于制备本发明所用骨架材料的其它金属离子、至少双配位的有机化合物、单配位物质及它们的制备方法,特别披露在EP-A 0 790 253、US 5,648,508和DE 10111230.0中。
关于特别可用于制备MOF-5的溶剂,除了以上参考文献中披露的溶剂以外,还可以使用二甲基甲酰胺、二乙基甲酰胺以及N-甲基吡咯烷酮,可以单独使用、相互结合使用或与其它溶剂结合使用。在骨架材料的制备中,尤其在MOF-5的制备中,可在结晶后回收溶剂和母液以节约成本和材料。
通过选择合适的有机配体和/或双配位化合物(即连接剂),可调节金属-有机骨架中孔的尺寸。一般来说,连接剂越大,孔的尺寸就越大。在主体(host)不存在及至少200℃的温度下仍得到金属-有机骨架支持的任何孔尺寸都是可以的。0.2nm到30nm的孔尺寸是优选的,而0.3nm到3nm的孔尺寸是特别优选的。
以下给出金属-有机骨架材料(MOFs)的示例以解释上文所述的一般概念。但给出这些具体示例并不是为了限制本发明的普遍性和保护范围。
通过举例的方式,给出如下已经合成和表征的金属-有机骨架材料的列表。其中也包括可用于本申请骨架中的新型等网状(isoreticular)金属-有机骨架材料(IR-MOFs)。关于这种具有相同骨架布局但呈现不同孔尺寸和晶体密度的材料的描述,例如可参见M.Eddouadi等人的Science 295(2002)469,这里将其引入本申请作为参考。
所用的溶剂对于这些材料的合成是特别重要的,因此将其列于表中。晶胞参数(角α、β、γ和间距a、b、c,间距以埃为单位)值由x射线衍射获得并代表在表中给出的空间群。
MOF-n | 组分摩尔比M+L | 溶剂S | α | β | γ | a | b | c | 空间群 |
MOF-0 | Zn(NO3)2·6H2OH3(BTC) | 乙醇 | 90 | 90 | 120 | 16.711 | 16.711 | 14.189 | P6(3)/Mcm |
MOF-2 | Zn(NO3)2·6H2O(0.246mmol)H2(BDC)(0.241mmol) | DMF甲苯 | 90 | 102.8 | 90 | 6.718 | 15.49 | 12.43 | P2(1)/n |
MOF-3 | Zn(NO3)2·6H2O(1.89mmol)H2(BDC)(1.93mmol) | DMFMeOH | 99.72 | 111.11 | 108.4 | 9.726 | 9.911 | 10.45 | P-1 |
MOF-4 | Zn(NO3)2·6H2O(1.00mmol)H3(BTC)(0.5mmol) | 乙醇 | 90 | 90 | 90 | 14.728 | 14.728 | 14.728 | P2(1)3 |
MOF-5 | Zn(NO3)2·6H2O(2.22mmol)H2(BDC)(2.17mmol) | DMF氯苯 | 90 | 90 | 90 | 25.669 | 25.669 | 25.669 | Fm-3m |
MOF-38 | Zn(NO3)2·6H2O(0.27mmol)H3(BTC)(0.15mmol) | DMF氯苯 | 90 | 90 | 90 | 20.657 | 20.657 | 17.84 | 14cm |
MOF-31Zn(ADC)2 | Zn(NO3)2·6H2O0.4mmolH2(ADC)0.8mmol | 乙醇 | 90 | 90 | 90 | 10.821 | 10.821 | 10.821 | Pn(-3)m |
MOF-12Zn2(ATC) | Zn(NO3)2·6H2O0.3mmolH4(ATC)0.15mmol | 乙醇 | 90 | 90 | 90 | 15.745 | 16.907 | 18.167 | Pbca |
MOF-20ZnNDC | Zn(NO3)2·6H2O0.37mmolH2NDC0.36mmol | DMF氯苯 | 90 | 92.13 | 90 | 8.13 | 16.444 | 12.807 | P2(1)/c |
MOF-37 | Zn(NO3)2·6H2O0.2mmolH2NDC0.2mmol | DEF氯苯 | 72.38 | 83.16 | 84.33 | 9.952 | 11.576 | 15.556 | P-1 |
MOF-8Tb2(ADC) | Tb(NO3)3·5H2O0.10mmolH2ADC0.20mmol | DMSOMeOH | 90 | 115.7 | 90 | 19.83 | 9.822 | 19.183 | C2/c |
MOF-9Tb2(ADC) | Tb(NO3)3·5H2O0.08mmolH2ADB0.12mmol | DMSO | 90 | 102.09 | 90 | 27.056 | 16.795 | 28.139 | C2/c |
MOF-6 | Tb(NO3)3·5H2O0.30mmolH2(BDC)0.30mmol | DMFMeOH | 90 | 91.28 | 90 | 17.599 | 19.996 | 10.545 | P21/c |
MOF-7 | Tb(NO3)3·5H2O0.15mmolH2(BDC)0.15mmol | H2O | 102.3 | 91.12 | 101.5 | 6.142 | 10.069 | 10.096 | P-1 |
MOF-69A | Zn(NO3)2·6H2O0.083mmol4,4’BPDC0.041mmol | DEFH2O2MeNH2 | 90 | 111.6 | 90 | 23.12 | 20.92 | 12 | C2/c |
MOF-69B | Zn(NO3)2·6H2O0.083mmol2,6-NCD0.041mmol | DEFH2O2MeNH2 | 90 | 95.3 | 90 | 20.17 | 18.55 | 12.16 | C2/c |
MOF-11Cu2(ATC) | Cu(NO3)2·2.5H2O0.47mmolH2ATC0.22mmol | H2O | 90 | 93.86 | 90 | 12.987 | 11.22 | 11.336 | C2/c |
MOF-11Cu2(ATC)脱水 | 90 | 90 | 90 | 8.4671 | 8.4671 | 14.44 | P42/mmc | ||
MOF-14Cu3(BTB) | Cu(NO3)2·2.5H2O0.28mmolH3BTB0.052mmol | H2ODMFEtOH | 90 | 90 | 90 | 26.946 | 26.946 | 26.946 | Im-3 |
MOF-32Cd(ATC) | Cd(NO3)2·4H2O0.24mmolH4ATC0.10mmol | H2ONaOH | 90 | 90 | 90 | 13.468 | 13.468 | 13.468 | P(-4)3m |
MOF-33Zn2(ATB) | ZnCl20.15mmolH4ATB0.02mmol | H2ODMFEtOH | 90 | 90 | 90 | 19.561 | 15.255 | 23.404 | Imma |
MOF-34Ni(ATC) | Ni(NO3)2·6H2O0.24mmolH4ATC0.10mmol | H2ONaOH | 90 | 90 | 90 | 10.066 | 11.163 | 19.201 | P212121 |
MOF-36Zn2(MTB) | Zn(NO3)2·4H2O0.20mmolH4MTB0.04mmol | H2ODMF | 90 | 90 | 90 | 15.745 | 16.907 | 18.167 | Pbca |
MOF-39Zn3O(HBTB) | Zn(NO3)2·4H2O0.27mmolH3BTB0.07mmol | H2ODMFEtOH | 90 | 90 | 90 | 17.158 | 21.591 | 25.308 | Pnma |
NO305 | FeCl2·4H2O5.03mmol蚁酸86.90mmol | DMF | 90 | 90 | 120 | 8.2692 | 8.2692 | 63.566 | R-3c |
NO306A | FeCl2·4H2O5.03mmol蚁酸86.90mmol | DEF | 90 | 90 | 90 | 9.9364 | 18.374 | 18.374 | Pbcn |
NO29类似MOF-0 | Mn(AC)2·4H2O0.46mmolH3BTC0.69mmol | DMF | 120 | 90 | 90 | 14.16 | 33.521 | 33.521 | P-1 |
BPR48A2 | Zn(NO3)2·6H2O0.012mmolH2BDC0.012mmol | DMSO甲苯 | 90 | 90 | 90 | 14.5 | 17.04 | 18.02 | Pbca |
BPR69B1 | Cd(NO3)2·4H2O0.0212mmolH2BDC0.0428mmol | DMSO | 90 | 98.76 | 90 | 14.16 | 15.72 | 17.66 | Cc |
BPR92A2 | Co(NO3)2·6H2O0.018mmolH2BDC0.018mmol | NMP | 106.3 | 107.63 | 107.2 | 7.5308 | 10.942 | 11.025 | P1 |
BPR95C5 | Cd(NO3)2·4H2O0.012mmolH2BDC0.36mmol | NMP | 90 | 112.8 | 90 | 14.460 | 11.085 | 15.829 | P2(1)/n |
CuC6H4O6 | Cu(NO3)2·2.5H2O0.370mmolH23BDC(OH)20.37mmol | DMF氯苯 | 90 | 105.29 | 90 | 15.259 | 14.816 | 14.13 | P2(1)/c |
M(BTC)类似MOF-0 | Co(SO4)H2O0.055mmolH3BTC0.037mmol | DMF | 与MOF-0相同 | ||||||
Tb(C6H4O6) | Tb(NO3)3·5H2O0.370mmolH2(C6H4O6)0.56mmol | DMF氯苯 | 104.6 | 107.9 | 97.147 | 10.491 | 10.981 | 12.541 | P-1 |
Zn(C2O4) | ZnCl20.370mmol草酸0.37mmol | DMF氯苯 | 90 | 120 | 90 | 9.4168 | 9.4168 | 8.464 | P(-3)1m |
Co(CHO) | Co(NO3)2·5H2O0.043mmol蚁酸1.60mmol | DMF | 90 | 91.32 | 90 | 11.328 | 10.049 | 14.854 | P2(1)/n |
Cd(CHO) | Cd(NO3)2·4H2O0.185mmol蚁酸0.185mmol | DMF | 90 | 120 | 90 | 8.5168 | 8.5168 | 22.674 | R-3c |
Cu(C3H2O4) | Cu(NO3)2·2.5H2O0.043mmol丙二酸0.192mmol | DMF | 90 | 90 | 90 | 8.366 | 8.366 | 11.919 | P43 |
Zn6(NDC)5MOF-48 | Zn(NO3)2·6H2O0.097mmol14NDC0.069mmol | DMF氯苯H2O2 | 90 | 95.902 | 90 | 19.504 | 16.482 | 14.64 | C2/m |
MOF-47 | Zn(NO3)2·6H2O0.185mmolH2(BDC[CH3]4)0.185mmol | DMF氯苯H2O2 | 90 | 92.55 | 90 | 11.303 | 16.029 | 17.535 | P2(1)/c |
MO25 | Cu(NO3)2·2.5H2O0.084mmolBPhDC0.085mmol | DMF | 90 | 112.0 | 90 | 23.880 | 16.834 | 18.389 | P2(1)/c |
Cu-Thio | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DEF | 90 | 113.6 | 90 | 15.4747 | 14.514 | 14.032 | P2(1)/c |
C1BDC1 | Cu(NO3)2·2.5H2O0.084mmolH2(BDCCl2)0.085mmol | DMF | 90 | 105.6 | 90 | 14.911 | 15.622 | 18.413 | C2/c |
MOF-101 | Cu(NO3)2·2.5H2O0.084mmolBrBDC0.085mmol | DMF | 90 | 90 | 90 | 21.607 | 20.607 | 20.073 | Fm3m |
Zn3(BTC)2 | ZnCl20.033mmolH3BTC0.033mmol | DMFEtOH加碱 | 90 | 90 | 90 | 26.572 | 26.572 | 26.572 | Fm-3m |
MOF-j | Co(CH3CO2)2·4H2O(1.65mmol)H3(BZC)(0.95mmol) | H2O | 90 | 112.0 | 90 | 17.482 | 12.963 | 6.559 | C2 |
MOF-n | Zn(NO3)2·6H2OH3(BTC) | 乙醇 | 90 | 90 | 120 | 16.711 | 16.711 | 14.189 | P6(3)/mcm |
PbBDC | Pb(NO3)2(0.181mmol)H2(BDC)(0.181mmol) | DMF乙醇 | 90 | 102.7 | 90 | 8.3639 | 17.991 | 9.9617 | P2(1)/n |
Znhex | Zn(NO3)2·6H2O(0.171mmol)H3BTB(0.114mmol) | DMFp-二甲苯乙醇 | 90 | 90 | 120 | 37.1165 | 37.117 | 30.019 | P3(1)c |
AS16 | FeBr20.927mmolH2(BDC)0.927mmol | 脱水DMF | 90 | 90.13 | 90 | 7.2595 | 8.7894 | 19.484 | P2(1)c |
AS27-2 | FeBr20.927mmolH3(BDC)0.464mmol | 脱水DMF | 90 | 90 | 90 | 26.735 | 26.735 | 26.735 | Fm3m |
AS32 | FeCl31.23mmolH2(BDC)1.23mmol | 脱水DMF乙醇 | 90 | 90 | 120 | 12.535 | 12.535 | 18.479 | P6(2)c |
AS54-3 | FeBr20.927BPDC0.927mmol | 脱水DMF正丙醇 | 90 | 109.98 | 90 | 12.019 | 15.286 | 14.399 | C2 |
AS61-4 | FeBr20.927mmolm-BDC0.927mmol | 脱水吡啶 | 90 | 90 | 120 | 13.017 | 13.017 | 14.896 | P6(2)c |
AS68-7 | FeBr20.927mmolm-BDC1.204mmol | 脱水DMF吡啶 | 90 | 90 | 90 | 18.3407 | 10.036 | 18.039 | Pca21 |
Zn(ADC) | Zn(NO3)2·6H2O0.37mmolH2(ADC)0.36mmol | DMF氯苯 | 90 | 99.85 | 90 | 16.764 | 9.349 | 9.635 | C2/c |
MOF-12Zn2(ATC) | Zn(NO3)2·6H2O0.30mmolH4(ATC)0.15mmol | 乙醇 | 90 | 90 | 90 | 15.745 | 16.907 | 18.167 | Pbca |
MOF-20ZnNDC | Zn(NO3)2·6H2O0.37mmolH2NDC0.36mmol | DMF氯苯 | 90 | 92.13 | 90 | 8.13 | 16.444 | 12.807 | P2(1)/c |
MOF-37 | Zn(NO3)2·6H2O0.20mmolH2NDC0.20mmol | DEF氯苯 | 72.38 | 83.16 | 84.33 | 9.952 | 11.576 | 15.556 | P-1 |
Zn(NDC)(DMSO) | Zn(NO3)2·6H2OH2NDC | DMSO | 68.08 | 75.33 | 88.31 | 8.631 | 10.207 | 13.114 | P-1 |
Zn(NDC) | Zn(NO3)2·6H2OH2NDC | 90 | 99.2 | 90 | 19.289 | 17.628 | 15.052 | C2/c | |
Zn(HPDC) | Zn(NO3)2·4H2O0.23mmolH2(HPDC)0.05mmol | DMFH2O | 107.9 | 105.06 | 94.4 | 8.326 | 12.085 | 13.767 | P-1 |
Co(HPDC) | Co(NO3)2·6H2O0.21mmolH2(HPDC)0.06mmol | DMFH2O/乙醇 | 90 | 97.69 | 90 | 29.677 | 9.63 | 7.981 | C2/c |
Zn3(PDC)2.5 | Zn(NO3)2·4H2O0.17mmolH2(HPDC)0.05mmol | DMF/ClBzH2O/TEA | 79.34 | 80.8 | 85.83 | 8.564 | 14.046 | 26.428 | P-1 |
Cd2(TPDC)2 | Cd(NO3)2·4H2O0.06mmolH2(HPDC)0.06mmol | 甲醇/CHPH2O | 70.59 | 72.75 | 87.14 | 10.102 | 14.412 | 14.964 | P-1 |
Tb(PDC)1.5 | Tb(NO3)2·5H2O0.21mmolH2(HPDC)0.034mm | DMFH2O/乙醇 | 109.8 | 103.61 | 100.14 | 9.829 | 12.11 | 14.628 | P-1 |
ZnDBP | Zn(NO3)2·6H2O0.05mmol磷酸二苄酯0.10mmol | MeOH | 90 | 93.67 | 90 | 9.254 | 10.762 | 27.93 | P2/n |
Zn3(BPDC) | ZnBr20.021mmol4,4’BPDC0.005mmol | DMF | 90 | 102.76 | 90 | 11.49 | 14.79 | 19.18 | P21/n |
CdBDC | Cd(NO3)2·4H2O0.100mmolH2(BDC)0.401mmol | DMFNa2SiO3(aq) | 90 | 95.85 | 90 | 11.2 | 11.11 | 16.71 | P21/n |
Cd-mBDC | Cd(NO3)2·4H2O0.009mmolH2(mBDC)0.018mmol | DMFMeNH2 | 90 | 101.1 | 90 | 13.69 | 18.25 | 14.91 | C2/c |
Zn4OBNDC | Zn(NO3)2·6H2O0.041mmolBNDC | DMFMeNH2H2O2 | 90 | 90 | 90 | 22.35 | 26.05 | 59.56 | Fmmm |
Eu(TCA) | Eu(NO3)3·6H2O0.14mmolTCA0.026mmol | DMF氯苯 | 90 | 90 | 90 | 23.325 | 23.325 | 23.325 | Pm-3n |
Tb(TCA) | Tb(NO3)3·6H2O0.069mmolTCA0.026mmol | DMF氯苯 | 90 | 90 | 90 | 23.272 | 23.272 | 23.372 | Pm-3n |
Formate | Ce(NO3)3·6H2O0.138mmol甲酸0.43mmol | H2O乙醇 | 90 | 90 | 120 | 10.668 | 10.667 | 4.107 | R-3m |
FeCl2·4H2O5.03mmol甲酸86.90mmol | DMF | 90 | 90 | 120 | 8.2692 | 8.2692 | 63.566 | R-3c | |
FeCl2·4H2O5.03mmol甲酸86.90mmol | DEF | 90 | 90 | 90 | 9.9364 | 18.374 | 18.374 | Pbcn | |
FeCl2·4H2O5.03mmol甲酸86.90mmol | DEF | 90 | 90 | 90 | 8.335 | 8.335 | 13.34 | P-31c | |
NO330 | FeCl2·4H2O0.50mmol甲酸8.69mmol | 甲酰胺 | 90 | 90 | 90 | 8.7749 | 11.655 | 8.3297 | Pnna |
NO332 | FeCl2·4H2O0.50mmol甲酸8.69mmol | DIP | 90 | 90 | 90 | 10.0313 | 18.808 | 18.355 | Pbcn |
NO333 | FeCl2·4H2O0.50mmol甲酸8.69mmol | DBF | 90 | 90 | 90 | 45.2754 | 23.861 | 12.441 | Cmcm |
NO335 | FeCl2·4H2O0.50mmol甲酸8.69mmol | CHF | 90 | 91.372 | 90 | 11.5964 | 10.187 | 14.945 | P21/n |
NO336 | FeCl2·4H2O0.50mmol甲酸8.69mmol | MFA | 90 | 90 | 90 | 11.7945 | 48.843 | 8.4136 | Pbcm |
NO13 | Mn(Ac)2·4H2O0.46mmol苯甲酸0.92mmol联吡啶0.46mmol | 乙醇 | 90 | 90 | 90 | 18.66 | 11.762 | 9.418 | Pbcn |
NO29类似MOF-0 | Mn(Ac)2·4H2O0.46mmolH3BTC0.69mmol | DMF | 120 | 90 | 90 | 14.16 | 33.521 | 33.521 | P-1 |
Mn(hfac)2(O2CC6H5) | Mn(Ac)2·4H2O0.46mmolHfac0.92mmol联吡啶0.46mmol | 醚 | 90 | 95.32 | 90 | 9.572 | 17.162 | 14.041 | C2/c |
BPR43G2 | Zn(NO3)2·6H2O0.0288mmolH2BDC0.0072mmol | DMFCH3CN | 90 | 91.37 | 90 | 17.96 | 6.38 | 7.19 | C2/c |
BPR48A2 | Zn(NO3)2·6H2O0.012mmolH2BDC0.012mmol | DMSO甲苯 | 90 | 90 | 90 | 14.5 | 17.04 | 18.02 | Pbca |
BPR49B1 | Zn(NO3)2·6H2O0.024mmolH2BDC0.048mmol | DMSO甲醇 | 90 | 91.172 | 90 | 33.181 | 9.824 | 17.884 | C2/c |
BPR56F1 | Zn(NO3)2·6H2O0.012mmolH2BDC0.024mmol | DMSO正丙醇 | 90 | 90.096 | 90 | 14.5873 | 14.153 | 17.183 | P2(1)/n |
BPR68D10 | Zn(NO3)2·6H2O0.0016mmolH3BTC0.0064mmol | DMSO苯 | 90 | 95.316 | 90 | 10.0627 | 10.17 | 16.413 | P2(1)/c |
BPR69B1 | Cd(NO3)2·4H2O0.0212mmolH2BDC0.0428mmol | DMSO | 90 | 98.76 | 90 | 14.16 | 15.72 | 17.66 | Cc |
BPR73E4 | Cd(NO3)2·4H2O0.006mmolH2BDC0.003mmol | DMSO甲苯 | 90 | 92.324 | 90 | 8.7231 | 7.0568 | 18.438 | P2(1)/n |
BPR76D5 | Zn(NO3)2·6H2O0.0009mmolH2BzPDC0.0036mmol | DMSO | 90 | 104.17 | 90 | 14.4191 | 6.2599 | 7.0611 | Pc |
BPR80B5 | Cd(NO3)2·4H2O0.018mmolH2BDC0.036mmol | DMF | 90 | 115.11 | 90 | 28.049 | 9.184 | 17.837 | C2/c |
BPR80H5 | Cd(NO3)2·4H2O0.027mmolH2BDC0.027mmol | DMF | 90 | 119.06 | 90 | 11.4746 | 6.2151 | 17.268 | P2/c |
BPR82C6 | Cd(NO3)2·4H2O0.0068mmolH2BDC0.202mmol | DMF | 90 | 90 | 90 | 9.7721 | 21.142 | 27.77 | Fdd2 |
BPR86C3 | Co(NO3)2·6H2O0.0025mmolH2BDC0.075mmol | DMF | 90 | 90 | 90 | 18.3449 | 10.031 | 17.983 | Pca2(1) |
BPR86H6 | Cd(NO3)2·6H2O0.010mmolH2BDC0.010mmol | DMF | 80.98 | 89.69 | 83.412 | 9.8752 | 10.263 | 15.362 | P-1 |
Co(NO3)2·6H2O | NMP | 106.3 | 107.63 | 107.2 | 7.5308 | 10.942 | 11.025 | P1 | |
BPR95A2 | Zn(NO3)2·6H2O0.012mmolH2BDC0.012mmol | NMP | 90 | 102.9 | 90 | 7.4502 | 13.767 | 12.713 | P2(1)/c |
CuC6F4O4 | Cu(NO3)2·2.5H2O0.370mmolH2BDC(OH)20.37mmol | DMF氯苯 | 90 | 98.834 | 90 | 10.9675 | 24.43 | 22.553 | P2(1)/n |
Fe Formic | FeCl2·4H2O0.370mmol甲酸0.37mmol | DMF | 90 | 91.543 | 90 | 11.495 | 9.963 | 14.48 | P2(1)/n |
Mg Formic | Mg(NO3)2·6H2O0.370mmol甲酸0.37mmol | DMF | 90 | 91.359 | 90 | 11.383 | 9.932 | 14.656 | P2(1)/n |
MgC6F4O6 | Mg(NO3)2·6H2O0.370mmolH2BDC(OH)20.37mmol | DMF | 90 | 96.624 | 90 | 17.245 | 9.943 | 9.273 | C2/c |
ZnC2H4BDCMOF-38 | ZnCl20.44mmolCBBDC0.261mmol | DMF | 90 | 94.714 | 90 | 7.3386 | 16.834 | 12.52 | P2(1)/n |
MOF-49 | ZnCl20.44mmolm-BDC0.261mmol | DMFCH3CN | 90 | 93.459 | 90 | 13.509 | 11.984 | 27.039 | P2/c |
MOF-26 | Cu(NO3)2·5H2O0.084mmolDCPE0.085mmol | DMF | 90 | 95.607 | 90 | 20.8797 | 16.017 | 26.176 | P2(1)/n |
MOF-112 | Cu(NO3)2·2.5H2O0.084mmolo-Br-m-BDC0.085mmol | DMF乙醇 | 90 | 107.49 | 90 | 29.3241 | 21.297 | 18.069 | C2/c |
MOF-109 | Cu(NO3)2·2.5H2O0.084mmolKDB0.085mmol | DMF | 90 | 111.98 | 90 | 23.8801 | 16.834 | 18.389 | P2(1)/c |
MOF-111 | Cu(NO3)2·2.5H2O0.084mmolo-BrBDC0.085mmol | DMF乙醇 | 90 | 102.16 | 90 | 10.6767 | 18.781 | 21.052 | C2/c |
MOF-110 | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DMF | 90 | 90 | 120 | 20.0652 | 20.065 | 20.747 | R-3/m |
MOF-107 | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DEF | 104.8 | 97.075 | 95.206 | 11.032 | 18.067 | 18.452 | P-1 |
MOF-108 | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DBF/甲醇 | 90 | 113.63 | 90 | 15.4747 | 14.514 | 14.032 | C2/c |
MOF-102 | Cu(NO3)2·2.5H2O0.084mmolH2(BDCCl2)0.085mmol | DMF | 91.63 | 106.24 | 112.01 | 9.3845 | 10.794 | 10.831 | P-1 |
C1bdc1 | Cu(NO3)2·2.5H2O0.084mmolH2(BDCCl2)0.085mmol | DEF | 90 | 105.56 | 90 | 14.911 | 15.622 | 18.413 | P-1 |
Cu(NMOP) | Cu(NO3)2·2.5H2O0.084mmolNBDC0.085mmol | DMF | 90 | 102.37 | 90 | 14.9238 | 18.727 | 15.529 | P2(1)/m |
Tb(BTC) | Tb(NO3)3·5H2O0.033mmolH3BTC0.033mmol | DMF | 90 | 106.02 | 90 | 18.6986 | 11.368 | 19.721 | |
Zn3(BTC)2Honk | ZnCl20.033mmolH3BTC0.033mmol | DMF乙醇 | 90 | 90 | 90 | 26.572 | 26.572 | 26.572 | Fm-3m |
Zn4O(NDC) | Zn(NO3)2·4H2O0.066mmol14NDC0.066mmol | DMF乙醇 | 90 | 90 | 90 | 41.5594 | 18.818 | 17.574 | aba2 |
CdTDC | Cd(NO3)2·4H2O0.014mmol噻吩0.040mmolDABCO0.020mmol | DMFH2O | 90 | 90 | 90 | 12.173 | 10.485 | 7.33 | Pmma |
IRMOF-2 | Zn(NO3)2·4H2O0.160mmolo-Br-BDC0.60mmol | DEF | 90 | 90 | 90 | 25.772 | 25.772 | 25.772 | Fm-3m |
IRMOF-3 | Zn(NO3)2·4H2O0.20mmolH2N-BDC0.60mmol | DEF乙醇 | 90 | 90 | 90 | 25.747 | 25.747 | 25.747 | Fm-3m |
IRMOF-4 | Zn(NO3)2·4H2O0.11mmol[C3H7O]2-BDC0.48mmol | DEF | 90 | 90 | 90 | 25.849 | 25.849 | 25.849 | Fm-3m |
IRMOF-5 | Zn(NO3)2·4H2O0.13mmol[C5H11O]2-BDC0.50mmol | DEF | 90 | 90 | 90 | 12.882 | 12.882 | 12.882 | Pm-3m |
IRMOF-6 | Zn(NO3)2·4H2O0.20mmol[C2H4]-BDC0.60mmol | DEF | 90 | 90 | 90 | 25.842 | 25.842 | 25.842 | Fm-3m |
IRMOF-7 | Zn(NO3)2·4H2O0.07mmol1,4NDC0.20mmol | DEF | 90 | 90 | 90 | 12.914 | 12.914 | 12.914 | Pm-3m |
IRMOF-8 | Zn(NO3)2·4H2O0.55mmol2,6NDC0.42mmol | DEF | 90 | 90 | 90 | 30.092 | 30.092 | 30.092 | Fm-3m |
IRMOF-9 | Zn(NO3)2·4H2O0.05mmolBPDC0.42mmol | DEF | 90 | 90 | 90 | 17.147 | 23.322 | 25.255 | Pnnm |
IRMOF-10 | Zn(NO3)2·4H2O0.02mmolBPDC0.012mmol | DEF | 90 | 90 | 90 | 34.281 | 34.281 | 34.281 | Fm-3m |
IRMOF-11 | Zn(NO3)2·4H2O0.05mmolHPDC0.20mmol | DEF | 90 | 90 | 90 | 24.822 | 24.822 | 56.734 | R-3m |
IRMOF-12 | Zn(NO3)2·4H2O0.017mmolHPDC0.12mmol | DEF | 90 | 90 | 90 | 34.281 | 34.281 | 34.281 | Fm-3m |
IRMOF-13 | Zn(NO3)2·4H2O0.048mmolPDC0.31mmol | DEF | 90 | 90 | 90 | 24.822 | 24.822 | 56.734 | R-3m |
IRMOF-14 | Zn(NO3)2·4H2O0.17mmolPDC0.12mmol | DEF | 90 | 90 | 90 | 34.381 | 34.381 | 34.381 | Fm-3m |
IRMOF-15 | Zn(NO3)2·4H2O0.063mmolTPDC0.025mmol | DEF | 90 | 90 | 90 | 21.459 | 21.459 | 21.459 | Im-3m |
IRMOF-16 | Zn(NO3)2·4H2O0.0126mmolTPDC0.05mmol | DEFNMP | 90 | 90 | 90 | 21.49 | 21.49 | 21.49 | Pm-3m |
Zn(NO3)2·4H2O0.20mmolDHBC0.10mmol | DEF异丙醇 | 90 | 90 | 120 | 25.9 | 25.9 | 6.8 | R-3 |
ADC 乙炔二羧酸
NDC 萘二羧酸
BDC 苯二羧酸
ATC 金刚烷四羧酸
BTC 苯三羧酸
BTB 三苯甲酸苯酯/盐
MTB 四苯甲酸甲酯/盐
ATB 四苯甲酸金刚酯/盐
ADB 二苯甲酸金刚酯/盐
BPDC 4,4-联苯二羧酸
DHBC 2,5-二羟基对苯二甲酸
合成这些材料的示例可以在例如J.Am.Chem.Soc.123(2001)第8241页以下或Acc.Chem.Res.31(1998)第474页以下见到。它们各自的相关内容完全引入本申请的内容中。
从结晶母液中分离骨架材料,特别是MOF-5,可以采用本领域中已知的方法进行,例如固-液分离、离心分离、萃取、过滤、膜式过滤、交叉流过滤、使用絮凝辅剂(非离子的、阴离子的和阳离子的辅剂)的絮凝;或通过添加诸如盐、酸或碱的pH调节剂;通过浮选;及通过在升高的温度下和/或在真空中蒸发母液以及浓缩固体。在这一步骤获得的材料通常是细小颗粒,不能用于需要成形体的大多数实际应用中,如用在催化剂中。
在本发明中,术语“成形体”是指至少具有二维外形并在至少一个空间方向上延伸至至少0.02mm的任意固体。只要该固体在一个方向上延伸至至少0.02mm,对其没有其它的限制,即该固体可以取任何可以想象的外形并可在任何方向上以任何长度延伸。在优选实施方案中,成形体在所有方向上延伸不超过50mm且不少于0.02mm。在更为优选的实施方案中,这一范围限制在1.5mm到5mm。
关于这些成形体的几何形状,球体或圆柱体是优选的,还可以是圆盘形的小片或任何其它合适的几何形状,例如蜂巢形、网状、中空体、线形排列等等。
为形成含有活性材料(例如催化活性的材料)的成形体,可采用数种途径。其中可提到的有:
(i)将活性材料单独地、或活性材料与粘合剂和/或其它组分的组合成型为成形体,例如通过造粒;
(ii)将活性材料施用到(多孔)载体上,和
(iii)将活性材料装载到多孔或非多孔基体上,然后将其成型为成形体。
虽然对制取含有本发明金属-有机骨架的成形体的途径没有限制,但在本文公开的发明中,上述途径是优选的。目前,沸石是最常用的可成型为成形体或可施用到(多孔)载体上的多孔活性材料。
关于制备含有至少一种金属-有机骨架材料的成形体的步骤,本领域技术人员已知的所有将粉末和/或微晶成型在一起的方法都是可以的。另外,所有将活性成分,如金属-有机骨架材料,施用到基体上的方法也是可以的。以下首先描述通过有关成型的方法制备成形体的过程,然后描述将所述材料施用到(多孔)基体上的方法。
在本发明中,术语“成型”是指本领域技术人员已知的任何方法,通过该方法,可以将不能满足上述对成形体要求的物质,即任何粉末、粉状物质、微晶排列等,制成在拟使用的条件下稳定的成形体。
将至少一种金属-有机骨架材料成型至成形体中的步骤是必不可少的,而根据本发明,以下步骤是可选择的:
(I)在成型之前可进行混合步骤,
(II)在成型之前可进行制备含有金属-有机骨架材料的糊状物或液体的步骤,例如可通过添加溶剂、粘合剂或其它附加物质,
(III)在成型之后可进行精加工的步骤,特别是干燥的步骤。
必不可少的成型、成形或形成的步骤可通过本领域技术人员已知的任何方法进行,以实现粉末、悬浮或糊状物的团聚。这些方法在例如Ullmann’sEnzylopdie der Technischen Chemie,第四版,Vol.2,1972第313页以下有描述,其各部分内容被引入本申请中以作参考。
一般可考虑以下几种主要的方法:(i)压块,即对粉状材料进行机械加压,其中使用或不使用粘合剂和/或其它添加剂,(ii)造粒(粒化),也就是使湿润的粉状材料经过旋转将其压紧,和(iii)烧结,也就是使材料经热处理而被压紧。后者对于本发明的材料来说在一定程度上是受限制的,因为该有机材料的热稳定性有限(见以下讨论)。
具体地说,根据本发明的成型步骤优选通过使用选自以下组的至少一种方法进行:使用活塞式压力机的压块、通过轧机加压的压块、无粘合剂压块、使用粘合剂的压块、粒化、混合、熔融、挤出、共挤出、旋转(spinning)、沉积、发泡、喷雾干燥、涂覆、造粒(特别是喷雾造粒或根据塑料加工领域内已知的任何方法进行的造粒),或者至少两种前述方法的任意组合。
优选的成型方法是那些通过在传统挤出机中挤出而进行的成型,例如可产生直径通常为约1到约10mm、特别是约1.5到约5mm的挤出物的挤出机。这种挤出设备在例如Ullmann’s Enzylopdie der TechnischenChemie,第四版,Vol.2,1972第313页以下有描述。除使用挤出机外,还优选将挤出压力机用于成型。
成型可以在提高的压力(其范围可从大气压力到几百巴)下、升高的温度(其范围可从室温到300℃)下或在保护性气氛(稀有气体、氮气或它们的混合物)中进行。这些条件的任意组合也是可行的。
成型步骤可以在粘合剂和/或其它能够使被团聚的材料稳定的附加物质的存在下进行。至于该至少一种可选择的粘合剂,可使用本领域技术人员已知的任何可提高需成型到一起的颗粒之间附着力的材料。可向金属-有机骨架材料添加粘合剂、可增强粘度的有机化合物和/或可将材料转变为糊状物的液体,随后可在混合设备或捏合设备或挤出机中将混合物压紧。然后可将获得的塑性材料成型,尤其可使用挤出压力机或挤出机,然后可以使获得的成型物经过可选择的精加工步骤(III),如干燥。
许多无机化合物都可用作粘合剂。例如,根据US-A 5,430,000,使用二氧化钛或水合的二氧化钛作粘合剂。其它现有技术中的粘合剂的示例有:
水合的氧化铝或其它含铝粘合剂(WO 94/29408);
硅化合物和铝化合物的混合物(WO 94/13584);
硅化合物(EP-A 0 592 050);
粘土矿物质(JP-A 03 037 156);
烷氧基硅烷(EP-B 0 012 544);
两亲性物质;
石墨。
其它可用的粘合剂原则上是迄今为止为了粘合粉状材料而使用的所有化合物。优选使用硅、铝、硼、磷、锆和/或钛的化合物,尤其是它们的氧化物。特别宜于作粘合剂的是二氧化硅,其中SiO2可以以二氧化硅溶胶的形式或以四烷氧基硅烷的形式引入成形步骤中。另外,还可以使用镁的氧化物、铍的氧化物和粘土(如微晶高岭石、高岭土、膨润土、多水高岭土、地开石、珍珠陶土和蠕陶土)作粘合剂。在本发明中,特别使用四烷氧基硅烷。具体示例有四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷和四丁氧基硅烷、类似的四烷氧基钛化合物和四烷氧基锆化合物及三甲氧基铝、三乙氧基铝、三丙氧基铝和三丁氧基铝,而四甲氧基硅烷和四乙氧基硅烷是特别优选的。
另外,可使用可增强粘度的有机物质和/或亲水性聚合物,如纤维素或聚丙烯酸酯。使用的可增强粘度的有机物质同样可以是任何适于此目的的物质。优选的是有机聚合物,特别是亲水性聚合物,例如纤维素、淀粉、聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯醇、聚乙烯基吡咯烷酮、聚异丁烯和聚四氢呋喃。这些物质主要是可以在捏合、成型和干燥步骤中通过连接初级颗粒而促进塑性材料的形成,并在成型及可选择的干燥过程中进一步确保成型物的机械稳定性。
关于用于可选择的混合步骤(I)或用于成型必不可少的步骤中的可产生糊状物的可选择的液体,则根本没有任何限制。除水之外,还可以使用醇,只要它们是可与水混溶的即可。因此,1到4个碳原子的单醇和可与水混溶的多元醇都可以使用。特别使用甲醇、乙醇、丙醇、正丁醇、异丁醇、叔丁醇及其中两种或多种的混合物。
胺或类胺化合物,例如四烷基铵化合物或氨基醇及含碳酸根的物质如碳酸钙,可用作其它的添加剂。这些另外的添加剂在EP-A 0 389 041、EP-A0 200 260和WO 95/19222中有描述,这里将它们全部引入本申请的内容中作为参考。
可通过干燥或加热(可选择在保护性气氛或真空中进行)将大部分(如果不是全部的话)上述添加的物质从成形体中除去。为了保持金属-有机骨架的完整,优选不将成形体暴露于超过300℃的温度下。但研究表明,在前述适中条件下的加热/干燥、特别是真空中的干燥、优选远低于300℃的温度足以至少将有机化合物移出金属-有机骨架的孔(参见上文给出的关于金属-有机骨架的参考)。通常根据使用的添加物质选择和适用这些条件。
添加组分(可选择的溶剂、粘合剂、添加剂、含有金属-有机骨架的材料)的顺序不是关键的。可以先加入粘合剂,然后是例如金属-有机骨架材料和需要时的添加剂,最后是含有至少一种醇和/或水的混合物;或者也可以互换任何前述组分的顺序。
关于混合例如含有金属-有机骨架的材料、粘合剂及可选择的其它加工材料(即附加的材料)的可选择的步骤(I),可采用材料处理和单元操作领域的技术人员已知的所有方法。如果混合是在液相中进行的,优选进行搅拌;如果被混合的固体是糊状的,优选进行捏合和/或挤出;如果被混合的组分都处于固态、粉末态,优选进行混合。还可以使用雾化器、喷雾器、扩散器或雾化器,如果使用的组分的状态允许使用这些设备的话。对于糊状和粉末状材料,优选使用静态混合器、行星式混合器、带有旋转容器的混合器、盘式混合器、叶轮式搅拌机、剪切盘混合器、离心混合器、混砂机、槽式捏合机、密闭式混合器、密闭式混合器和连续捏合机。可以肯定地说,混合的方法可能就足以实现成型,即混合步骤与成型步骤同时进行。
本发明的成形体优选以至少以下性质之一为特征:
(i)在至少一个空间方向上延伸至少0.02mm,并且在任何空间方向上延伸都不超过50mm。
(ii)为小片形并且直径在1.5mm到5mm的范围、高度在1mm到5mm的范围。
(iii)其抗压能力(压碎强度)在2N到100N的范围。
作为生产含有至少一种金属-有机骨架材料的成形体的次要途径,将所述材料施用到基体上的方法也是本发明的一部分。基体优选是多孔的。原则上,所有用于使所述材料与所述基体接触的技术都是可行的。具体而言,所有用于使活性材料与在催化剂的制备中已知的多孔基体接触的技术都可适用。
该至少一种接触方法选自含有以下方法的组:用液体浸渍、在液体中浸泡、喷雾、从液相中沉积、从气相中沉积(气相沉积)、沉淀、共沉淀、浸沾技术、涂覆。
关于多孔载体,本领域技术人员已知的各种成形体都可使用,只要成形体在其几何外形方面满足本发明中指出的一般要求即可,例如,满足上文给出的(i)到(iii)点中的要求。具体而言,将与金属-有机骨架材料接触的多孔基体可选自包含以下物质的组:氧化铝、活化的氧化铝、水合氧化铝、二氧化硅凝胶、硅酸盐、硅藻土、高岭土、氧化镁、活化的木炭、二氧化钛、沸石。
尽管使用多孔基体是优选的实施方案,但还可以使活性材料(金属-有机骨架)与非多孔体和/或二维基体接触。在将催化活性材料施用到非多孔成形体的情况下,可得到外壳催化剂。这种构造以及整体结构的实施方案毫无疑问可包括在本发明中,只要它们包含至少一种金属-有机骨架材料即可。
催化剂技术中常见的其它实施方案,例如在修补基面涂层(wash-coat)中施用活性物质和/或将载体构造成蜂巢形或孔道形或其它骨架形,是优选的。
本发明的成形体可用于技术人员已知的多孔体或带有孔道的物体相对于固体或粉末更具优势的任何方法中。这些应用特别包括:催化剂、催化剂载体、吸附作用载体、液体存储载体、干燥剂、离子交换材料、分子筛(分离器)、用于色谱法的材料、用于选择性释放和/或摄取分子的材料、分子识别、纳米管、纳米反应器。
在优选的应用中,本发明的成形体用作固定床/填料床反应器中的催化剂。原则上,所述成形体可用于气相反应中或固态成形体悬浮于浆液的液相反应中。原则上,本发明的成形体可用来催化技术人员已知的所有这些反应:已知或确信成形体中存在的孔道和/或孔和/或活性中心可以提高所述反应的活性和/或选择性和/或产率。
现在通过下列实施例进一步说明本发明,但这些实施例并不是为了限制本发明的保护范围。
实施例1(MOF-5的制备)
原材料 | 摩尔量 | 计算值 | 试验值 |
对苯二甲酸 | 12.3mmol | 2.04g | 2.04g |
四水合硝酸锌 | 36.98mmol | 9.67g | 9.68g |
二乙基甲酰胺(Merck) | 2568.8mmol | 282.2g | 282.2g |
将上表中给出的各种量的原材料按照二乙基甲酰胺、对苯二甲酸和硝酸锌的顺序溶解在烧杯中。将所得溶液引入两个内壁分别涂有特氟隆的高压釜(250ml)中。
结晶在105℃下进行20小时。随后,将橙色溶剂从黄色结晶中倒出,再将所述结晶用20ml二甲基甲酰胺浸没,再将后者倒出。将该过程重复三次。然后,将20ml氯仿倒在固体上,并用所述溶剂将该固体洗涤倾析两次。
将仍然潮湿的结晶(14.4g)引入真空设备,先在室温下真空(10-4mbar)中干燥,之后在120℃下干燥。
然后,通过X射线粉末衍射及微孔吸附测定描述所得产物的特征。测定的其对氩的吸附等温线(87K;Micromeritics ASAP 2010)呈现I-型等温线,这是微孔材料的特征。它还具有按照朗缪尔计算为3020m2/g的比表面积,及0.97ml/g的微孔体积(在p/p0=0.4的相对压力下)。
实施例2:MOF材料的制备
将2,5-二羟基对苯二甲酸(19mg、0.10mmol)和Zn(NO3)2·4H2O(53mg、0.20mmol)溶于DMF(2.0mL)、PrOH(0.10mL)和水(0.10mL)的混合溶液中,然后将其放入耐热玻璃试管(10mm×70mm)中。然后将试管冷冻并抽空,在真空下火封。以2℃/min的速度将试管加热到105℃,保持20小时,然后以2℃/min的速度冷却至室温。收集黄色针状结晶,并用DMF(3×5mL)洗涤。产率:26mg,基于2,5-二羟基对苯二甲酸为81%。
实施例3(含有MOF-5的小片的制备)
使用Korsch提供的偏心压力机(EK0型)压制本发明的小片。这里,选择的形成小片的工具是带有一个直径为4.75mm孔的结构,这样,就可以形成直径为4.75mm的小片。送入偏心压力机的混合物由99.8%的MOF-2和0.2%的石墨组成,即49.9g MOF-5粉末和0.1g石墨。这两种成分已在混合烧瓶中完全混合。该过程在氮气气氛中进行。
对偏心压力机作如下调整:(i)填充高度:10mm,(ii)上冲头刺入深度:7mm及(iii)转子每分钟转动的圈数:20。
小片的形状如下:(i)直径:4.75mm且(ii)高度:3mm。
制成小片后,用Zwick的硬度分级设备测量侧压抗压强度(压碎强度),为10N/小片,标准误差为0.8N/小片。
Claims (12)
1、一种金属-有机骨架材料,含有孔、至少一种金属离子及至少一种至少双配位的与所述金属离子配位键联的有机化合物,其特征在于该材料是成形体的形式。
2、根据权利要求1的金属-有机骨架材料,其特征在于成形体在至少一个空间方向上延伸至少0.02mm,并在任何空间方向上延伸不超过50mm。
3、根据权利要求1或2的金属-有机骨架材料,其特征在于成形体为小片形,并且其直径为1.5mm到5mm、高度为1mm到5mm。
4、根据前述权利要求任一项的金属-有机骨架材料,其特征在于其抗压强度,即压碎强度,为2到100N。
5、生产根据前述权利要求任一项的形式为成形体的金属-有机骨架材料的方法,其特征在于成形体是通过至少一个成型步骤获得的。
6、根据权利要求5的方法,其特征在于所述至少一个成型步骤选自以下方法的组:使用活塞式压力机的压块、通过轧机加压的压块、无粘合剂的压块、使用粘合剂的压块、粒化、混合、熔融、挤出、共挤出、旋转、沉积、发泡、喷雾干燥、涂覆、造粒及喷雾造粒。
7、根据权利要求5或6的方法,其特征在于向金属-有机骨架材料中添加至少一种粘合剂,并且该至少一种粘合剂选自包括以下物质的组:水合的氧化铝或其它含铝粘合剂、硅化合物和铝化合物的混合物、硅化合物、粘土矿物质、烷氧基硅烷、两亲性物质和石墨。
8、生产根据权利要求1到4任一项的形式为成形体的金属-有机骨架材料的方法,其特征在于成形体是通过使至少一种金属-有机骨架材料与至少一种基体接触而得到的。
9、根据权利要求8的方法,其特征在于所述至少一种接触方法选自由以下方法组成的组:用液体浸渍、在液体中浸泡、喷雾、从液相中沉积、从气相中沉积即气相沉积、沉淀、共沉淀、浸沾技术、涂覆。
10、根据权利要求5到9任一项的方法,其特征在于所述成形体具有至少一种以下特征:(i)成形体为整体结构,(ii)成形体为二维体,(iii)金属-有机骨架材料为修补基面涂层的一部分,(iv)成形体具有类似骨架或类似蜂巢的结构。
11、根据权利要求1到4任一项的金属-有机骨架材料的用途,用于固定床或填料床反应器中,或用于所述成形体悬浮于浆料中的液相反应中。
12、根据权利要求1到4任一项的金属-有机骨架材料的用途,用作催化剂、催化剂载体,用于吸附、液体存储,用做干燥剂、离子交换材料、分子筛即分离物质、用于色谱法的材料、用于选择性释放和/或摄取分子的材料、用于分子识别、纳米管、纳米反应器。
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CN107549871A (zh) * | 2017-09-06 | 2018-01-09 | 重庆市江北区健希环保新材料科技有限公司 | 一种消除香烟或空气中有害物质的组合物及其用途 |
CN107576701A (zh) * | 2017-09-05 | 2018-01-12 | 济南大学 | 一种多孔金属有机框架物负载Ag纳米复合材料的制备方法和应用 |
CN107674088A (zh) * | 2017-09-19 | 2018-02-09 | 太原理工大学 | 一种多孔复合骨架材料的浆态合成方法 |
CN108290134A (zh) * | 2015-11-27 | 2018-07-17 | 巴斯夫欧洲公司 | 金属-有机骨架的超快高空时产率合成 |
CN110143943A (zh) * | 2019-05-15 | 2019-08-20 | 中国石油大学(华东) | 一种钡基配合物及其制备方法和在荧光识别领域的应用 |
CN110694301A (zh) * | 2019-11-05 | 2020-01-17 | 武汉谱立科技有限公司 | 液相色谱柱及其制备方法和其填料的制备方法 |
CN113272053A (zh) * | 2019-01-29 | 2021-08-17 | 埃克森美孚研究工程公司 | 金属-有机骨架挤出材料及其制造方法 |
CN113578273A (zh) * | 2021-07-28 | 2021-11-02 | 长三角(义乌)生态环境研究中心 | 金属有机框架膜的制备方法 |
CN115023284A (zh) * | 2019-11-26 | 2022-09-06 | 埃克森美孚技术与工程公司 | 金属-有机材料挤出物、制造方法和使用方法 |
Families Citing this family (158)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6754485B1 (en) * | 1998-12-23 | 2004-06-22 | American Calcar Inc. | Technique for effectively providing maintenance and information to vehicles |
DE60213579T2 (de) * | 2001-04-30 | 2007-08-09 | The Regents Of The University Of Michigan, Ann Arbor | Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung |
EP1513612A2 (en) * | 2002-06-19 | 2005-03-16 | University Of Iowa Research Foundation | Gas storage materials and devices |
US7652132B2 (en) * | 2003-05-09 | 2010-01-26 | The Regents Of The University Of Michigan | Implementation of a strategy for achieving extraordinary levels of surface area and porosity in crystals |
US7309380B2 (en) * | 2003-06-30 | 2007-12-18 | Basf Aktiengesellschaft | Gas storage system |
US20050004404A1 (en) | 2003-07-03 | 2005-01-06 | Basf Akiengesellschaft | Process for the alkoxylation of monools in the presence of metallo-organic framework materials |
DE10355087A1 (de) * | 2003-11-24 | 2005-06-09 | Basf Ag | Verfahren zur elektrochemischen Herstellung eines kristallinen porösen metallorganischen Gerüstmaterials |
CN1914219A (zh) * | 2003-12-05 | 2007-02-14 | 密歇根大学董事会 | 金属有机多面体 |
US7411081B2 (en) | 2004-01-13 | 2008-08-12 | Basf Aktiengesellschaft | Process for preparing and organometallic framework material |
KR101227824B1 (ko) | 2004-10-22 | 2013-01-30 | 더 리젠츠 오브 더 유니버시티 오브 미시간 | 공유 결합 유기물의 골격구조들 및 폴리헤드라 |
US7524444B2 (en) * | 2004-11-09 | 2009-04-28 | Basf Aktiengesellschaft | Shaped bodies containing metal-organic frameworks |
JP5113321B2 (ja) * | 2005-02-08 | 2013-01-09 | 本田技研工業株式会社 | 有被膜錯体凝集体の製造方法 |
PT1874459E (pt) | 2005-04-07 | 2016-02-08 | Univ Michigan | Alta adsorção de gás numa estrutura microporosa organometálica com locais metálicos abertos |
DE102005022844A1 (de) * | 2005-05-18 | 2006-11-23 | Basf Ag | Abtrennung von Geruchsstoffen aus Gasen |
DE102005023856A1 (de) * | 2005-05-24 | 2006-11-30 | Basf Ag | Verfahren zur Herstellung poröser metall-organischer Gerüstmaterialien |
DE102005023857A1 (de) * | 2005-05-24 | 2006-11-30 | Basf Ag | Suspension zur Verminderung von Geruch |
JP4882295B2 (ja) * | 2005-07-19 | 2012-02-22 | トヨタ自動車株式会社 | ガス吸蔵タンクの製造方法 |
US8628055B2 (en) * | 2005-07-27 | 2014-01-14 | The Board Of Trustees Of The University Of Illinois | Bi-direction rapid action electrostatically actuated microvalve |
DE102005035762A1 (de) * | 2005-07-29 | 2007-02-01 | Süd-Chemie AG | Hochporöse Schichten aus MOF-Materialien und Verfahren zur Herstellung derartiger Schichten |
DE102005037893A1 (de) * | 2005-08-10 | 2007-02-15 | Süd-Chemie AG | Verfahren zur Herstellung hochaktiver Metall/Metalloxid-Katalysatoren |
US7897920B2 (en) * | 2005-09-21 | 2011-03-01 | Analog Devices, Inc. | Radiation sensor device and method |
WO2007038508A2 (en) * | 2005-09-26 | 2007-04-05 | The Regents Of The University Of Michigan | Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room-temperature |
EP1948353A2 (en) * | 2005-10-06 | 2008-07-30 | The Board Of Trustees Of The University Of Illinois | High gain selective preconcentrators |
US8123834B2 (en) * | 2005-10-06 | 2012-02-28 | The Board Of Trustees Of The University Of Illinois | High gain selective metal organic framework preconcentrators |
DE102005056564B4 (de) | 2005-11-25 | 2009-11-12 | Gkss-Forschungszentrum Geesthacht Gmbh | Polymerelektrolytmembran mit Koordinationspolymer, Verfahren zu seiner Herstellung sowie Verwendung in einer Brennstoffzelle |
WO2007090864A1 (de) | 2006-02-10 | 2007-08-16 | Basf Se | Verfahren zur herstellung poröser organischer gerüstmaterialien |
CN101432070A (zh) | 2006-02-28 | 2009-05-13 | 密歇根大学董事会 | 官能化沸石骨架的制备 |
KR100806586B1 (ko) * | 2006-03-10 | 2008-02-28 | 한국화학연구원 | 수분의 흡착 및 탈착을 위한 흡착제 |
US20070256976A1 (en) * | 2006-04-10 | 2007-11-08 | Boyes Barry E | Metal-coated sorbents as a separation medium for HPLC of phosphorus-containing materials |
US7880026B2 (en) | 2006-04-14 | 2011-02-01 | The Board Of Trustees Of The University Of Illinois | MOF synthesis method |
US20090092818A1 (en) * | 2006-04-18 | 2009-04-09 | Basf Se | Organometallic aluminum fumarate backbone material |
US7441574B2 (en) * | 2006-08-17 | 2008-10-28 | The Goodyear Tire & Rubber Company | Pneumatic tire |
DE102006039581B4 (de) * | 2006-08-23 | 2017-07-06 | Mahle International Gmbh | Kraftstofffilter |
US20080111114A1 (en) * | 2006-10-30 | 2008-05-15 | Gilbert Alan M | Flame-retardant materials and systems |
US9017584B2 (en) * | 2006-10-30 | 2015-04-28 | Alan M. Gilbert | Flame-retardant materials and systems |
US9719019B1 (en) | 2006-10-30 | 2017-08-01 | Alan M. Gilbert | Flame-retardant materials and systems |
US8603225B2 (en) | 2006-10-30 | 2013-12-10 | Basf Se | Aluminum naphthalenedicarboxylate as porous metal-organic framework material |
US7985868B1 (en) | 2006-11-01 | 2011-07-26 | Sandia Corporation | Hybrid metal organic scintillator materials system and particle detector |
JP2010510881A (ja) * | 2006-11-27 | 2010-04-08 | コリア リサーチ インスティテュート オブ ケミカル テクノロジー | 多孔性有機−無機ハイブリッド体の製造方法、前記方法によって得られる有機−無機ハイブリッド体及びその触媒的使用 |
WO2008075951A1 (en) | 2006-12-21 | 2008-06-26 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Device for the removal of toxic substances from blood |
EP2079660B1 (en) | 2007-01-03 | 2017-01-11 | Insilico Co., Ltd. | Coordination polymer crystal with porous metal-organic frameworks and preperation method thereof |
US20100143693A1 (en) * | 2007-01-24 | 2010-06-10 | The Regents Of The University Of California | Crystalline 3d- and 2d covalent organic frameworks |
US8372779B2 (en) | 2007-04-24 | 2013-02-12 | Basf Se | Metal organic frameworks based on aluminum, iron and chromium |
EP2155608A4 (en) * | 2007-05-11 | 2011-01-12 | Univ California | MULTI-COMPONENT GAS ADSORPTION GAS SEPARATION |
EP2152826B1 (en) * | 2007-05-24 | 2013-07-17 | Basf Se | Chemical-mechanical polishing composition comprising porous metal-organic framework materials |
KR100907907B1 (ko) * | 2007-07-16 | 2009-07-16 | 주식회사 인실리코텍 | 다공성 금속-유기 골격 구조를 갖는 배위중합체 화합물 및 이의 용매 함유물 |
WO2009011545A2 (en) * | 2007-07-16 | 2009-01-22 | Insilicotech Co., Ltd. | Compound or solvate thereof with mesoporous metal-organic framework |
US8480792B2 (en) * | 2007-07-17 | 2013-07-09 | The Regents Of The University Of California | Preparation of functionalized zeolitic frameworks |
US9132411B2 (en) | 2007-08-30 | 2015-09-15 | The Regents Of The University Of Michigan | Strategies, linkers and coordination polymers for high-performance sorbents |
US8383545B2 (en) * | 2007-08-30 | 2013-02-26 | The Regents Of The University Of Michigan | Strategies, linkers and coordination polymers for high-performance sorbents |
US8222179B2 (en) * | 2007-08-30 | 2012-07-17 | The Regents Of The University Of Michigan | Porous coordination copolymers and methods for their production |
ES2713194T3 (es) * | 2007-09-25 | 2019-05-20 | Univ California | Entramados organometálicos comestibles y biocompatibles |
DE202008000810U1 (de) * | 2007-11-04 | 2008-12-24 | BLüCHER GMBH | Sorptionsfiltermaterial |
US8034952B2 (en) * | 2007-11-15 | 2011-10-11 | University Of South Florida | Supramolecular assemblies and building blocks |
EP2072117A1 (en) | 2007-12-19 | 2009-06-24 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Sorbent material |
DE102008010774A1 (de) | 2007-12-21 | 2009-06-25 | Cam-D Technologies Gmbh | Grenzflächenaktive Metallkomplexe zur Adsorption von Schadstoffen sowie Verfahren zu ihrer Herstellung |
DE102008010775A1 (de) * | 2007-12-21 | 2009-06-25 | Cam-D Technologies Gmbh | Grenzflächenaktive Metallkomplexe auf Trägermaterialien zur Adsorption von Schadstoffen sowie Verfahren zur Herstellung der geträgerten Materialien |
US8123841B2 (en) * | 2008-01-16 | 2012-02-28 | The Board Of Trustees Of The University Of Illinois | Column design for micro gas chromatograph |
KR20100118580A (ko) * | 2008-01-24 | 2010-11-05 | 바스프 에스이 | 건조제로서의 다공성 금속-유기 구조 물질 |
EP2087916A1 (en) | 2008-02-11 | 2009-08-12 | ICinnovation BV | Electrosorption device for the purification of blood and other fluids |
US8142745B2 (en) * | 2008-02-21 | 2012-03-27 | Exxonmobil Research And Engineering Company | Separation of carbon dioxide from nitrogen utilizing zeolitic imidazolate framework materials |
US8142746B2 (en) * | 2008-02-21 | 2012-03-27 | Exxonmobil Research And Engineering Company | Separation of carbon dioxide from methane utilizing zeolitic imidazolate framework materials |
US8071063B2 (en) * | 2008-02-21 | 2011-12-06 | Exxonmobile Research And Engineering Company | Separation of hydrogen from hydrocarbons utilizing zeolitic imidazolate framework materials |
US8269029B2 (en) | 2008-04-08 | 2012-09-18 | The Board Of Trustees Of The University Of Illinois | Water repellent metal-organic frameworks, process for making and uses regarding same |
US8557214B2 (en) * | 2008-05-15 | 2013-10-15 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona | Porous metal oxide particles |
WO2009149381A2 (en) * | 2008-06-05 | 2009-12-10 | The Regents Of University Of California | Chemical framework compositions and methods of use |
CN102105421B (zh) | 2008-07-21 | 2013-09-25 | 巴斯夫欧洲公司 | 工业分离丙烯的方法 |
KR101007183B1 (ko) * | 2008-10-23 | 2011-01-12 | 제일모직주식회사 | 탄소나노튜브 합성용 담지촉매, 그 제조방법 및 이를 이용한 탄소나노튜브 |
US9512145B2 (en) | 2008-12-18 | 2016-12-06 | The Regents Of The University Of California | Porous reactive framework |
WO2010078337A1 (en) | 2008-12-29 | 2010-07-08 | The Regents Of The University Of California | A gas sensor incorporating a porous framework |
US8674128B2 (en) | 2009-01-15 | 2014-03-18 | The Regents Of The University Of California | Conductive organometallic framework |
EP2384237A1 (en) | 2009-02-02 | 2011-11-09 | The Regents of The University of California | Reversible ethylene oxide capture in porous frameworks |
EP2230288B1 (de) * | 2009-03-20 | 2016-05-25 | Basf Se | Metallorganische gerüstmaterialien in kälte/wärmemaschinen |
US8876953B2 (en) | 2009-06-19 | 2014-11-04 | The Regents Of The University Of California | Carbon dioxide capture and storage using open frameworks |
US8916722B2 (en) | 2009-06-19 | 2014-12-23 | The Regents Of The University Of California | Complex mixed ligand open framework materials |
EP2403815A1 (en) | 2009-07-27 | 2012-01-11 | The Regents of The University of California | Oxidative homo-coupling reactions of aryl boronic acids using a porous copper metal-organic framework as a highly efficient heterogeneous catalyst |
US8633331B2 (en) * | 2009-09-10 | 2014-01-21 | Research Foundation Of The City University Of New York | Nanocomposite materials comprising metal-organic-framework units and methods of using same |
EP2467388A4 (en) | 2009-09-25 | 2014-12-17 | Univ California | OPEN METAL ORGANIC STRUCTURES WITH EXCEPTIONAL SURFACE AREA AND LARGE GAS STORAGE CAPACITY |
US9308511B2 (en) | 2009-10-14 | 2016-04-12 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using thixotropic gels |
FR2951722B1 (fr) | 2009-10-23 | 2011-11-11 | Inst Francais Du Petrole | Nouveau materiau hybride organique-inorganique ihm-2 et procedes de preparation |
US9688700B2 (en) | 2009-11-30 | 2017-06-27 | Basf Se | Metal-organic frameworks based on on 2,5-furandicarboxylic acid or 2,5-thiophenedicarboxylic acid |
WO2011068830A2 (en) | 2009-12-01 | 2011-06-09 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Porous geopolymer materials |
KR101663184B1 (ko) * | 2009-12-15 | 2016-10-06 | 삼성전자주식회사 | 하이브리드 다공성 물질 및 그의 제조방법 |
US8425662B2 (en) | 2010-04-02 | 2013-04-23 | Battelle Memorial Institute | Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, and gas separation assemblies |
US10106437B2 (en) | 2010-07-07 | 2018-10-23 | Tusaar Inc. | Metal removal system |
MX2013000469A (es) | 2010-07-20 | 2013-02-11 | Basf Se | Funcionalizacion de moleculas organicas usando estructuras de metal-organicas (mofs) como catalizadores. |
US9365691B2 (en) | 2010-08-06 | 2016-06-14 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using intrepenetrating inorganic-organic composite gels |
US8506782B2 (en) | 2010-08-13 | 2013-08-13 | Southwest Research Institute | Electrophoretic deposition of adsorbent media |
CA2812294A1 (en) | 2010-09-27 | 2012-06-21 | The Regents Of The University Of California | Conductive open frameworks |
US8524932B2 (en) | 2010-09-30 | 2013-09-03 | Basf Se | Process for preparing porous metal-organic frameworks based on aluminum fumarate |
RU2013130865A (ru) * | 2010-12-07 | 2015-01-20 | Басф Се | Способ нанесения на несущую поверхность покрытий с пористой металлорганической структурой |
WO2012100224A2 (en) | 2011-01-21 | 2012-07-26 | The Regents Of The University Of California | Preparation of metal-triazolate frameworks |
JP2014507431A (ja) | 2011-02-04 | 2014-03-27 | ザ リージェンツ オブ ザ ユニバーシティー オブ カリフォルニア | 金属カテコレート骨格体の製造 |
WO2012138750A2 (en) * | 2011-04-04 | 2012-10-11 | Massachusetts Institute Of Technology | Methods for electrochemically induced cathodic deposition of crystalline metal-organic frameworks |
KR20140035379A (ko) * | 2011-04-21 | 2014-03-21 | 바스프 에스이 | 다공성 방향족 골격(paf) 물질을 함유하는 성형체 |
DE102011076080A1 (de) | 2011-05-18 | 2012-11-22 | Technische Universität Dresden | Verfahren zur Herstellung von Partikeln enthaltend Metall-organische Gerüstverbindungen |
JP5795195B2 (ja) * | 2011-06-06 | 2015-10-14 | 昭栄化学工業株式会社 | 多孔性金属錯体の製造方法 |
KR101273877B1 (ko) | 2011-08-16 | 2013-06-25 | 한국화학연구원 | 결정성 하이브리드 나노세공체 분말을 포함하는 복합체 및 그 제조방법 |
US9192913B2 (en) | 2011-09-05 | 2015-11-24 | Kuraray Co., Ltd. | Adsorbent |
EP2758355B1 (en) | 2011-09-21 | 2023-05-10 | Arizona Board of Regents, a Body Corporate of the State of Arizona acting for and on behalf of Arizona State University | Process for preparing geopolymer materials |
EP2766046B1 (en) | 2011-10-13 | 2017-08-02 | The Regents of The University of California | Metal-organic frameworks with exceptionally large pore aperatures |
WO2013059785A1 (en) | 2011-10-21 | 2013-04-25 | Massachusetts Institute Of Technology | Adsorption system |
CA2859042A1 (en) * | 2011-12-23 | 2013-06-27 | Tusaar Inc. | System for dynamic fluidized loading of a ligand upon carbon media and methods associated therewith |
WO2013158484A1 (en) | 2012-04-18 | 2013-10-24 | King Abdullah University Of Science And Technology | Electrode separator |
JP5945805B2 (ja) * | 2012-07-31 | 2016-07-05 | 昭栄化学工業株式会社 | 複合触媒材料及びその製造方法 |
JP6204737B2 (ja) * | 2012-07-31 | 2017-09-27 | 昭栄化学工業株式会社 | 炭化水素の製造方法及びクラッキング触媒 |
FR2995308B1 (fr) * | 2012-09-12 | 2014-08-29 | IFP Energies Nouvelles | Procede de preparation d'un mof mis en forme avec un liant hydraulique par pastillage sans liquide ou par granulation presentant des proprietes mecaniques ameliorees |
EP2897929A4 (en) | 2012-09-19 | 2016-06-01 | Basf Se | ACETYLENE BRIDGING BOND SEQUENCES AND METALLO-ORGANIC STRUCTURES (MOF) PRODUCED THEREFROM |
WO2014107726A1 (en) * | 2013-01-07 | 2014-07-10 | Northeastern University | Non-noble metal catalysts for oxygen depolarized cathodes and their uses |
EP2950920A1 (en) | 2013-01-31 | 2015-12-09 | Basf Se | Metal-organic framework extrudates with high packing density and tunable pore volume |
WO2014118054A1 (en) * | 2013-01-31 | 2014-08-07 | Basf Se | Stable spherical, porous metal-organic framework shaped bodies for gas storage and gas separation |
FR3002939B1 (fr) | 2013-03-07 | 2016-01-01 | IFP Energies Nouvelles | Procede de preparation d'un materiau hybride organique-inorganique mis en forme avec un liant polymere |
WO2015006010A2 (en) | 2013-06-21 | 2015-01-15 | Dong-Kyun Seo | Metal oxides from acidic solutions |
WO2015012068A1 (ja) * | 2013-07-26 | 2015-01-29 | 昭和電工株式会社 | 炭化水素吸着用成形体 |
WO2015054332A1 (en) * | 2013-10-10 | 2015-04-16 | Corning Incorporated | Composite honeycombs for gas storage |
US10035127B2 (en) | 2013-11-04 | 2018-07-31 | The Regents Of The University Of California | Metal-organic frameworks with a high density of highly charged exposed metal cation sites |
CN106029674B (zh) | 2014-02-19 | 2020-02-14 | 加利福尼亚大学董事会 | 耐酸性、耐溶剂性、以及耐热性金属有机骨架 |
US10494386B2 (en) | 2014-03-18 | 2019-12-03 | The Regents Of The University Of California | Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks |
CN106459590B (zh) | 2014-03-27 | 2019-11-05 | 巴斯夫欧洲公司 | 包含金属有机骨架材料的多孔膜 |
WO2015195179A2 (en) | 2014-03-28 | 2015-12-23 | The Regents Of The University Of California | Metal organic frameworks comprising a plurality of sbus with different metal ions and/or a plurality of organic linking ligands with different functional groups. |
WO2015166015A1 (en) * | 2014-04-30 | 2015-11-05 | Imec Vzw | Method of producing a thin metal-organic framework film using vapor phase precursors |
WO2015171791A1 (en) | 2014-05-06 | 2015-11-12 | Massachusetts Institute Of Technology | Compositions and methods comprising conductive metal organic frameworks and uses thereof |
AU2015273283B2 (en) * | 2014-06-10 | 2020-03-19 | Cambridge Enterprise Limited | Metal-organic frameworks |
WO2015191962A1 (en) | 2014-06-12 | 2015-12-17 | Arizona Board Of Regents On Behalf Of Arizona State University | Carbon dioxide adsorbents |
US10196887B2 (en) | 2014-07-15 | 2019-02-05 | Halliburton Energy Services, Inc. | Metal-organic frameworks as porous proppants |
EP2985075A1 (en) | 2014-08-15 | 2016-02-17 | Basf Se | Shaped body made of a porous material |
WO2016075100A1 (en) | 2014-11-11 | 2016-05-19 | Basf Se | Storage vessel comprising layers of a shaped body of a porous solid separated by a seal |
US10118877B2 (en) | 2014-12-03 | 2018-11-06 | The Regents Of The University Of California | Metal-organic frameworks for aromatic hydrocarbon separations |
WO2016135133A1 (en) | 2015-02-27 | 2016-09-01 | Basf Se | A vehicle comprising a storage system and a combustion engine, the storage system comprising a container and at least one storage vessel |
JP6578704B2 (ja) * | 2015-03-31 | 2019-09-25 | 東ソー株式会社 | 多孔性配位高分子 |
JP6522397B2 (ja) * | 2015-04-03 | 2019-05-29 | 株式会社クラレ | 多孔性金属錯体ペレットの製造方法 |
EP3283439A4 (en) * | 2015-04-11 | 2018-09-26 | Northwestern University | Metal-organic frameworks for adsorption of liquid phase compounds |
US10723635B2 (en) * | 2015-04-11 | 2020-07-28 | Northwestern University | Metal-organic frameworks for adsorption of liquid phase compounds |
EP3093550A1 (en) | 2015-05-11 | 2016-11-16 | Basf Se | Storage vessel comprising at least one shaped body of a porous solid |
EP3093549A1 (en) | 2015-05-11 | 2016-11-16 | Basf Se | Vehicle comprising an internal combustion engine, at least one storage vessel and a cooling chamber and/or an air condition unit |
US10058855B2 (en) | 2015-05-14 | 2018-08-28 | The Regents Of The University Of California | Redox-active metal-organic frameworks for the catalytic oxidation of hydrocarbons |
EP3130834A1 (en) | 2015-08-13 | 2017-02-15 | Basf Se | A vehicle comprising a storage system and a combustion engine, the storage system comprising a container and at least two storage vessels |
EP3130835A1 (en) | 2015-08-13 | 2017-02-15 | Basf Se | A vehicle comprising a storage system and a combustion engine, the storage system comprising a container and at least one storage vessel surrounded by a housing |
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Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1554574A (en) * | 1976-11-15 | 1979-10-24 | Ici Ltd | Treatment of solid transition metal compound and use of the product in an olefine polymerisation catalyst |
US5601437A (en) | 1994-10-17 | 1997-02-11 | Methode Electronics, Inc. | Clockspring with centering display device |
US5648508A (en) | 1995-11-22 | 1997-07-15 | Nalco Chemical Company | Crystalline metal-organic microporous materials |
JP3740242B2 (ja) | 1996-02-29 | 2006-02-01 | 英史 平井 | 新規な複合体およびその製造方法、ならびに該複合体からなる一酸化炭素吸着剤 |
JPH09290151A (ja) * | 1996-04-26 | 1997-11-11 | Osaka Gas Co Ltd | 化学物質吸着材及びその製造方法 |
JPH1066865A (ja) * | 1996-08-28 | 1998-03-10 | Osaka Gas Co Ltd | 難燃性ガス貯蔵剤、難燃性ガス貯蔵方法ならびに高圧難燃性ガス発生装置 |
US6372932B1 (en) | 1997-07-25 | 2002-04-16 | University Of Liverpool | Porous solid products of 1,3,5-benzenetricarboxylate and metal ions |
US6384253B1 (en) * | 1999-10-01 | 2002-05-07 | Illinois Institute Of Technology | Composite materials |
DE10111230A1 (de) * | 2001-03-08 | 2002-09-19 | Basf Ag | Metallorganische Gerüstmaterialien und Verfahren zu deren Herstellung |
DE60213579T2 (de) | 2001-04-30 | 2007-08-09 | The Regents Of The University Of Michigan, Ann Arbor | Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung |
US20030078311A1 (en) * | 2001-10-19 | 2003-04-24 | Ulrich Muller | Process for the alkoxylation of organic compounds in the presence of novel framework materials |
US6929679B2 (en) * | 2002-02-01 | 2005-08-16 | Basf Aktiengesellschaft | Method of storing, uptaking, releasing of gases by novel framework materials |
-
2002
- 2002-05-30 US US10/157,182 patent/US6893564B2/en not_active Expired - Lifetime
-
2003
- 2003-05-27 KR KR1020047019328A patent/KR101004304B1/ko not_active IP Right Cessation
- 2003-05-27 WO PCT/EP2003/005546 patent/WO2003102000A1/en active Application Filing
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- 2003-05-27 EP EP03735469.3A patent/EP1513849B1/en not_active Expired - Lifetime
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- 2003-05-28 MY MYPI20031962A patent/MY138593A/en unknown
- 2003-05-30 TW TW092114793A patent/TWI273922B/zh not_active IP Right Cessation
-
2004
- 2004-12-08 IS IS7588A patent/IS7588A/is unknown
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Also Published As
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EP1513849A1 (en) | 2005-03-16 |
WO2003102000A1 (en) | 2003-12-11 |
JP2005528204A (ja) | 2005-09-22 |
ES2594616T3 (es) | 2016-12-21 |
AU2003237689A8 (en) | 2003-12-19 |
MXPA04011225A (es) | 2005-01-25 |
CA2487873A1 (en) | 2003-12-11 |
EP1513849B1 (en) | 2016-07-13 |
TWI273922B (en) | 2007-02-21 |
US20030222023A1 (en) | 2003-12-04 |
AU2003237689A1 (en) | 2003-12-19 |
MY138593A (en) | 2009-07-31 |
KR101004304B1 (ko) | 2010-12-28 |
IS7588A (is) | 2004-12-08 |
TW200403101A (en) | 2004-03-01 |
US6893564B2 (en) | 2005-05-17 |
CA2487873C (en) | 2012-07-24 |
CN1331868C (zh) | 2007-08-15 |
KR20050008749A (ko) | 2005-01-21 |
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