WO2017158165A1 - Method for the preparation of metal organic frameworks - Google Patents
Method for the preparation of metal organic frameworks Download PDFInfo
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- WO2017158165A1 WO2017158165A1 PCT/EP2017/056404 EP2017056404W WO2017158165A1 WO 2017158165 A1 WO2017158165 A1 WO 2017158165A1 EP 2017056404 W EP2017056404 W EP 2017056404W WO 2017158165 A1 WO2017158165 A1 WO 2017158165A1
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- 238000000034 method Methods 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 title description 117
- 230000008569 process Effects 0.000 claims abstract description 93
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 32
- 239000013110 organic ligand Substances 0.000 claims abstract description 30
- 239000013141 crystalline metal-organic framework Substances 0.000 claims abstract description 22
- 238000001694 spray drying Methods 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 146
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- 229910001868 water Inorganic materials 0.000 claims description 54
- 239000013207 UiO-66 Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000011324 bead Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 239000013291 MIL-100 Substances 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001540 azides Chemical class 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- 239000007921 spray Substances 0.000 description 91
- 239000000243 solution Substances 0.000 description 57
- 238000000634 powder X-ray diffraction Methods 0.000 description 56
- 239000000843 powder Substances 0.000 description 37
- 238000001878 scanning electron micrograph Methods 0.000 description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 29
- 238000005119 centrifugation Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 22
- 239000012467 final product Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000003153 chemical reaction reagent Substances 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000012530 fluid Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 14
- 230000004913 activation Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000012856 packing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
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- 230000035484 reaction time Effects 0.000 description 7
- 238000004729 solvothermal method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- IMBBXSASDSZJSX-UHFFFAOYSA-N 4-Carboxypyrazole Chemical compound OC(=O)C=1C=NNC=1 IMBBXSASDSZJSX-UHFFFAOYSA-N 0.000 description 5
- 239000012917 MOF crystal Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000013115 Zn-MOF-74 Substances 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- 239000013118 MOF-74-type framework Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000013341 scale-up Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- QRYQYPQYYQPROM-BUOKYLHBSA-J (e)-but-2-enedioate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)\C=C\C([O-])=O.[O-]C(=O)\C=C\C([O-])=O QRYQYPQYYQPROM-BUOKYLHBSA-J 0.000 description 2
- -1 -CSSH Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XWHGTQGLZJRYNB-UHFFFAOYSA-N 2-acetamidoterephthalic acid Chemical compound CC(=O)NC1=CC(C(O)=O)=CC=C1C(O)=O XWHGTQGLZJRYNB-UHFFFAOYSA-N 0.000 description 2
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012922 MOF pore Substances 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000011469 building brick Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004891 diazines Chemical class 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JIIUWPYGXWLJRT-UHFFFAOYSA-N 4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid Chemical compound C1CC2=CC(C(=O)O)=CC3=C2C2=C1C=C(C(O)=O)C=C2CC3 JIIUWPYGXWLJRT-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 description 1
- QURGMSIQFRADOZ-UHFFFAOYSA-N 5-(3,5-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 QURGMSIQFRADOZ-UHFFFAOYSA-N 0.000 description 1
- LQEZHWGJSWHXPJ-UHFFFAOYSA-N 5-(4-carboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C(O)=O)=CC(C(O)=O)=C1 LQEZHWGJSWHXPJ-UHFFFAOYSA-N 0.000 description 1
- KMWCSNCNHSEXIF-UHFFFAOYSA-N 5-methyl-1h-imidazole-4-carbaldehyde Chemical compound CC=1N=CNC=1C=O KMWCSNCNHSEXIF-UHFFFAOYSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- 229910052695 Americium Inorganic materials 0.000 description 1
- 229910016962 As(SH)3 Inorganic materials 0.000 description 1
- 229910017258 AsO4H Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 229910052685 Curium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 description 1
- 229910005942 Ge(OH)3 Inorganic materials 0.000 description 1
- 229910005927 Ge(SH)4 Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
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- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910052766 Lawrencium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910013722 M(NO3)2 Inorganic materials 0.000 description 1
- 229910052764 Mendelevium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052781 Neptunium Inorganic materials 0.000 description 1
- 229910004841 P(SH)3 Inorganic materials 0.000 description 1
- 229910018830 PO3H Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910007215 Si(SH)4 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XTAARPJDFFXHGH-GRPBBMKTSA-N [(5s,8r,9s,10s,13s,14s,17s)-10,13-dimethyl-3-oxo-1,2,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-17-yl] propanoate Chemical compound C([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](OC(=O)CC)[C@@]2(C)CC1 XTAARPJDFFXHGH-GRPBBMKTSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-L naphthalene-2,6-dicarboxylate Chemical compound C1=C(C([O-])=O)C=CC2=CC(C(=O)[O-])=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-L 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- OTAJGWQCQIEFEV-UHFFFAOYSA-N pyrene-2,7-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=C2C=CC3=CC(C(=O)O)=CC4=CC=C1C2=C43 OTAJGWQCQIEFEV-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- TXXHDPDFNKHHGW-ZPUQHVIOSA-N trans,trans-muconic acid Chemical compound OC(=O)\C=C\C=C\C(O)=O TXXHDPDFNKHHGW-ZPUQHVIOSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Definitions
- the present invention is related to the field of material chemistry, particularly, metal organic chemistry.
- the invention provides a method for the industrial preparation of metal organic frameworks.
- MOFs Metal organic frameworks, also termed MOFs, form an interesting class of microporous or mesoporous substances having characteristics which allow their use in many technical fields, such as storage, separation or controlled release of chemical substances, catalysis and drug delivery. These potential applications are a direct consequence of the porous architecture of MOFs, which leads to high specific surface area of these materials.
- MOFs are composed of two major components: a metal ion or cluster of metal ions and an organic molecule that plays the role of a ligand.
- the organic units are typically di-, tri- or polydentate ligands.
- the choice of metal and organic ligand has significant effects on the structure and properties of the MOF. For example, the metal coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal and in which orientation.
- MOFs are produced almost exclusively by hydrothermal or solvothermal techniques, where crystals are slowly grown from a hot solution of metal precursor, such as metal salts, and bridging ligands. Since ligands in MOFs typically bind reversibly, the usual slow growth of crystals allows defects to be redissolved, resulting in a material with milli- and micrometer-scale crystals and a near-equilibrium defect density.
- WO2010058123 and EP1070 538 disclose methods for hydrothermal preparation of MOFs.
- US20100076220 discloses a process for the obtaining of crystalline porous metal organic compounds in a liquid phase at elevated temperature.
- MOFs for industrial applications, such as storage materials for consumer products, demands an immense scale-up of their synthesis.
- Most of the available methodologies imply the use of high temperatures, high pressure and long crystallization times. The required conditions thus obstruct considerably the scale-up of MOF preparation which is required for industrial application.
- EP2764004 disclosed large-scale MOF production at mild conditions and good yields.
- Said process comprises spray drying a metal ion and an organic ligand which is at least bidentate into a spray dryer in the presence of a solvent.
- Reaction times needed for the synthesis of MOFs are thereby greatly reduced and dry crystalline MOFs, such as HKUST-1 and other Cu-based MOFs, are provided directly out of the initial liquid reagents (without the need of filtering and drying).
- dry crystalline MOFs such as HKUST-1 and other Cu-based MOFs
- the inventors have developed an alternative spray-drying process which allows for rapid, large-scale production at mild conditions of a wide variety of MOFs, some of which could not be obtained at these advatageous conditions by prior art methods, or were obtained with low yields and/or poor quality.
- the new method comprises first subjecting the reagents to a short activating step before spray-drying the activated reagents to form the dry, crystaline MOF.
- the first aspect of the invention relates to a process for the preparation of dry crystalline metal organic frameworks which comprises:
- step b) spray drying the mixture obtained from step a) under conditions
- FIG 19 shows a schematic representation of a particular embodiment of the method of the invention.
- the reagents are activated forming Secondary Building Units (SBU) which are more suitable starting points for synthesis of different types of MOF which are based in complex and large SBUs, such as oxoclusters in the case of UiO-66 series or helical rods in the CPO-27 family, opening the way to mass production of these industrially relevant materials. Selecting the optimal combination of conditions at which appropriate activation of the reagents is achieved is crucial for obtaining good quality MOF at high yields.
- SBU Secondary Building Units
- Sub-optimal conditions will either not achieve formation of the required SBU or will promote growth of the MOF crystal thus interfering with the spray-drying of the (over-) activated solution (step b).
- Over-activation during step a) may stopple the spray-dryer's noozle, reduce the yield and/or result in poor quality MOF. Under-activation will result in poor quality MOF and/or a poor yield, or even no MOF at all.
- the activation and spray-drying may be performed in continuous flow.
- the whole process may be continuous by installing a continuous unloading system for collecting the dry crystalline MOF (step c).
- the process of the invention of course has all the advantages described for the prior spray-drying method: mild conditions, regular industrial equipment, drastically reduced reaction times and reduced dimensions of the obtained MOFs. Altogether, the process is scalable, clean, economical and
- the present process has the advantage of improving crystallinity of MOF particles.
- the obtained MOFs are usually in the form of spherical beads of size comprised from 0.1 to 400 ⁇ .
- Such beads are compact tiny particles, highly robust and difficult to break which cannot be obtained by means previously disclosed.
- the resulting product has the advantage of possessing surprisingly high MOF particle density, in addition to intrinsically high specific surface area, which translates into higher absorption capacity when compared to prior art products. While having such high MOF density, the product of the invention is also
- a second aspect of the invention refers to crystalline metal organic frameworks obtained by the process as defined above.
- Such MOFs are preferably in the form of spherical beads, usually of size comprised from 0.1 to 400 pm.
- the crystals directly obtained by the process of the invention may have purity up to 99% (w/w). Additional washing and drying steps result in substantially pure crystals.
- the process of the invention contributes to MOF quality and increases production ease and yield.
- FIG. 1 a) X-ray powder diffraction (XRPD) pattern of Zr-1 ,4-BDC (also known as UiO-66) obtained according to the invention (upper pattern) and simulated pattern of UiO-66 obtained by solvothermal method reported in the literature (Cavka S. S. Y. et al) (lower pattern), b) Scanning Electron Microscopy (SEM) image of the spherical superstructure of Zr-1 ,4-BDC of the invention.
- XRPD X-ray powder diffraction
- UiO-66 also known as UiO-66
- FIG 2 a) XRPD pattern of Zr-1 ,4-BDC-NH2 (UiO-66-NH2) obtained according to the invention ( example 1 .2) (upper pattern) and bare UiO-66 reported in the literature (Cavka S. S. Y., et al, lower pattern), b) SEM image for the Zr- 1 ,4-BDC-NH2 obtained according to the invention (example 1 .2).
- FIG 3 a) XRPD pattern of the Zr-1 ,4-BDC-Br (also known as UiO-66-Br) obtained according to the invention (upper pattern) and bare UiO-66 reported in the literature (Cavka S. S.
- FIG 4 a) XRPD pattern of the UiO-66-(OH) 2 obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, lower pattern), b) SEM image of the UiO-66- (OH) 2 obtained according to the invention.
- FIG 5 a) XRPD pattern of the Zr-NDC obtained according to the invention
- FIG 6 a) XRPD pattern of UiO-66-NO 2 obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-NO 2 obtained according to the invention.
- FIG. 7 a) XRPD pattern of Zr-1 ,4-BDC-Acetamido (UiO-66-Acetamido) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-Acetamido obtained according to the invention.
- FIG. 8 a) XRPD pattern of Zr-1 ,4-NDC (UiO-66-1 ,4-NDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO- 66-1 ,4-NDC obtained according to the invention.
- FIG. 9 a) XRPD pattern of [Ni 8 (OH) 4 (H 2 O)2(L)6]n obtained according to the invention (upper pattern) compared with the bare [Ni 8 (OH) 4 (H 2 O)2(L)6]n reported in the literature (Padial, et al, lower pattern), b) SEM image of the [Ni 8 (OH) 4 (H 2 O)2(L)6]n obtained according to the invention
- FIG. 10 a) XRPD pattern of UiO-66-(BDC-Br) 0 5 (BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66- (BDC-Br) 0 5 (BDC) obtained according to the invention.
- FIG. 11 a) XRPD pattern of UiO-66-(BDC-Br)(BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-
- FIG. 12 a) XRPD pattern of UiO-66-(BDC-Br) 2 (BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-
- FIG. 13 a) XRPD pattern of UiO-66-(BDC-Br)(BDC)(NH 2 -BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-(BDC-Br)(BDC)(NH 2 -BDC) obtained according to the invention.
- FIG. 14 a) XRPD pattern of Fe-1 ,3,5-BTC obtained according to the invention (upper pattern) compared with the simulated powder pattern for Fe-1 ,3,5- BTC.
- FIG. 15 a) XRPD pattern of CPO-27-Zn obtained according to the invention (upper pattern) compared to the CPO-27-Zn synthesized by the solvothermal method reported in the literature (Rosi N. L, et al, lower pattern), b) SEM image of the CPO-27-Zn obtained according to the invention.
- FIG. 16 a) XRPD pattern of CPO-27-Co obtained according to the invention (upper pattern) compared to the CPO-27-Co reported in the literature
- FIG. 17 a) XRPD pattern of CPO-27-Ni obtained according to the invention (upper pattern) compared to the CPO-27-Ni reported in the literature (Dietzel, P. D. C, et al, 2006, lower pattern), b) SEM image of the CPO-27-Ni obtained according to the invention.
- FIG. 18 a) XRPD pattern of CPO-27-Cu obtained according to the invention (upper pattern) compared to the CPO-27-Zn synthesized by the solvothermal method reported in the literature (Rosi N.
- FIG. 19 Schematic representation of the synthesis of a MOF UiO-66 according to the invention. ⁇ , activation; SD, spray srying; 1 , reagents; 2, secondary building unit; 3, UiO-66 crystal.
- FIG 20 a) XRPD pattern of Zr-1 ,4-BDC-NH2 (UiO-66-NH2) obtained according to the invention (example 6) (upper pattern) and bare UiO-66 reported in the literature (Cavka S. S. Y., et al, lower pattern), b) SEM image for the Zr-1 ,4-BDC-NH2 obtained according to the invention (example 6).
- FIG 21 a) XRPD pattern of MOF-801 obtained according to the invention (example 7) (upper pattern) and bare MOF-801 reported in the literature (Furukawa H, et al, lower pattern), b) SEM image for the MOF-801 obtained according to the invention (example 7).
- the invention is related to a facile, rapid and scalable method for the synthesis of MOFs, including complex MOFs, in a continuous flow reactor coupled to the spray dryer, combining the benefits of both systems as efficient mass and heat transfer during the continuous flow zone (activation step) and the possibility to confine the synthesis in individual reactors (atomized droplets) for the assembly of the MOF (growth step).
- Metal Organic Frameworks also termed MOFs, are crystalline compounds consisting of metal ions coordinated to often rigid organic molecules to form one-, two-, or three-dimensional structures that are highly porous.
- organic ligand which is at least bidentate it is understood an organic compound that is able to bind at least two metal ions through coordination bonds.
- spray also known as atomizing refers to the process of forming a spray, which is a dynamic collection of drops dispersed in a gas.
- a "spray dryer” is a device well known in the state of the art where a liquid input stream is sprayed in small droplets through a nozzle (or atomizer) into a hot gas stream.
- activating in the sense of the present invention it is meant the process by which the reagents form Secondary Building Units (SBUs).
- SBUs are molecular complexes and cluster entities in which ligand coordination modules and metal coordination environments can be utilized in the
- the MOFs obtained by the process of the invention are usually in the form of tiny spherical beads with surprisingly high MOF density which translates in surprisingly high absorption capacity.
- the size of these beads is usually from 0.1 to 400 pm.
- spherical beads it is meant particles of spherical or quasi-spherical morphology.
- the beads are thus not necessarily perfect spheres but may be substantially spherical particles, i.e. comparable to a sphere.
- the term "bead” in the context of the present invention further implies that the particles are stuffed, i.e. they are not empty capsules but sound compact particles entirely formed by MOFs. Obtaining such high density MOF beads by a rapid, clean scalable and economical process has not been previously described.
- the term "size" refers to a characteristic physical dimension.
- the size of the microcapsule corresponds to the diameter of the sphere or the equivalent diameter of the quasi-sphere assimilated as a sphere.
- the state of the art provides appropriate techniques and equipments to calculate the diameter of particles and in particular of spheres or substantially spherical particles.
- the diameter can be measured using laser diffraction analysis.
- the size (diameter) of the beads of the invention may be calculated from their images, for example from SEM images, by hand or applying an appropriate imaging software such as Gatan microscopy suite software.
- a size of a set of beads can refer to a mode of a distribution of sizes, such as a peak size of the distribution of sizes.
- optimal conditions for the activating step are required to efficiently form SBUs that enable further synthesis of MOFs by spray-drying.
- conditions in the activating step a) of the process of the invention are contacting at least one metal ion and at least one organic ligand which is at least bidentate in the presence of a solvent at a
- the contacting temperature is comprised from 70 to 150 °C, or from 80 to 140 °C, or from 90 to 130 °C, or from 90 to 120 °C, or from 100 to 125 °C or from 100 to 120 °C, or from 100 to 1 15 °C, or from 1 10 to 120 °C, or from 80 to 1 15 °C, or from 80 to 1 10 °C, or from 90 to 1 10 °C, or from 85 to 105 °C, or from 80 to 100 °C, or from 90 to 100 °C.
- the contacting step is performed during a time comprised from 20 to 1 10 s, or from 30 to 90 s, or from 40 to 80 s, or from 50 to 90 s, or from 50 to 70 s, or from 40 to 50 s, or from 50 to 60 s, or from 60 to 70 s, or from 70 to 80 s.
- the metal ions for use in the process of the invention are those usually employed for the preparation of MOFs.
- Non-limiting metal ions are those from chemical elements in the following groups: alkali metals (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), transition metals (Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg) and post-transition metals (Al, Ga, In, TI, Sn, Pb, Bi), as well as metalloids (B, Si, Ge, As, Sb, Te, Po), lanthanides (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and actin
- the at least one metal ion is selected from the group consisting of Zr, Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Zr, Gd, Eu, Tb, and mixtures thereof. In a preferred embodiment the at least one metal ion is selected from the group consisting of Zr, Zn, Cu, Fe, Gd, Mg, and mixtures thereof.
- the metal ion is provided as a compound which is a source of a metal ion, usually a salt.
- metal salts for use in the invention are nitrates, chlorides, sulphates, acetates, hydroxides, oxides, acetylacetonates, bromides, carbonates, carboxylates, tartrates and perchlorates.
- MOF formation can take place by reacting more than one metal ion. In one embodiment the process of the invention is performed by reacting between one and six different metal ions. In a preferred
- the process of the invention is performed by reacting between one and three different metal ions. In a more preferred embodiment the process of the invention is performed by reacting between one and two different metal ions.
- the MOF can be synthesized by reacting two metal ions with at least one organic ligand which is at least bidentate according to the present invention. According to the invention it is also possible that the MOF is formed by the reaction of one or more metal ions with one or more organic ligands.
- the process of the invention is performed by reacting between one and six organic ligands which are at least bidentate. In a preferred embodiment the process of the invention is performed by reacting from one to three organic ligands which are at least bidentate. In a more preferred embodiment the process of the invention is performed by reacting from one to two organic ligands which are at least bidentate.
- the metal ion or ions coordinate with one or more organic compounds that act like a ligand.
- the organic ligands in the sense of the present invention must be at least bidentate, meaning that they must be able to bind at least two metal ions by coordination bonds.
- the organic ligands according to the invention can be bidentate, but also tridentate, tetradentate or pluridentate in the sense that they may coordinate two, three, four or multiple metal ions through coordination bonds.
- the organic ligand coordinates between 2 and 20 metal ions.
- the organic ligand coordinates between 2 and 12 metal ions.
- the organic ligand coordinates between 2 and 8 metal ions.
- Non-limiting functional groups that can be contained by the organic ligand to form a MOF according to the invention are -COOH, -CSSH, -NO 2 , - B(OH) 2 , -SO3H, -Ge(OH) 3 , -Sn(OH) 3 , -Si(SH) 4 , -Ge(SH) 4 , -Sn(SH) 3 , -PO3H, - AsOsH, -AsO 4 H, -P(SH) 3 , As(SH) 3 , C 4 H 2 O 4 , -RSH, -RNH 2 , -RNR-, -ROH, -
- the at least one organic ligand which is at least bidentate contains functional groups selected from the group consisting of a
- Preferred heterocycles contain O, S and/or N.
- Non-limiting examples of preferred heterocycles in the sense of the invention are azoles, pyridines and diazines.
- the at least one organic ligand which is at least bidentate may be comprised of at least one functional group as mentioned above bound to any suitable organic compound, provided that it is ensured that the organic ligand is capable of coordinating at least two metal ions.
- the at least one organic ligand which is at least bidentate is a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, imidazole, or mixtures thereof.
- the at least one organic ligand which is at least bidentate is selected from the group consisting of formic acid, acetic acid, oxalic acid, propanoic acid, butanedioic acid, (E)-butenedioic acid, benzene- 1 ,4-dicarboxylic acid, benzene-1 ,3-dicarboxylic acid, benzene-1 ,3,5- tricarboxylic acid, 2-amino-1 ,4-benzenedicarboxylic acid, 2-bromo-1 ,4- benzenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, biphenyl-3,3',5,5'- tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, 2,5-dihydroxy-1 ,4- benzenedicarboxylic acid, 1 ,3,5-tris(4-carboxyphenyl)
- the at least organic ligand which is at least bidentate is a peptide.
- the process of the invention requires that a solvent is present for the reagents to form the MOF.
- solvent relates to individual solvents and also to mixtures of different solvents.
- the solvent can be any aqueous or non-aqueous solvent. In certain embodiments of the invention, mixtures of two or more solvents are used.
- the solvent is selected from the group consisting of water, (C1 -C6)-alcohols, (C5-C7)- alkanes, alkenes, (C3-C8)-cycloalkanes, N, A/-di methyl formamide (DMF), ⁇ /,/V-diethyl formamide (DEF), dimethyl sulfoxide (DMSO), dioxane, chloroform, dichloromethane, diethyl ether, acetonitrile, toluene, benzene, tetrahydrofuran (THF), chlorobenzene, ethylene glycol, and mixtures thereof.
- DMF A/-di methyl formamide
- DEF ⁇ /,/V-diethyl formamide
- DMSO dimethyl sulfoxide
- dioxane chloroform, dichloromethane, diethyl ether, acetonitrile, toluene, benzene, t
- Preferred alcohols are methanol, ethanol and isopropanol.
- Preferred alkanes are hexane, heptane and pentane.
- the solvent is selected from water, ethanol, DMF and mixtures thereof.
- the conditions for the activation step comprise water as the solvent, a contacting temperature comprised from from 80 to 1 15 °C and a contacting time comprise from 30 to 90 s.
- the conditions for the activation step comprise water as the solvent, a contacting temperature comprised from from 80 to 100 °C and a contacting time comprise from 30 to 90 s.
- the conditions for the activation step comprise ethanol as the solvent, a contacting temperature comprised from from 80 to 1 15 °C and a contacting time comprise from 30 to 90 s.
- the conditions for the activation step comprise a mixture of water and ethanol as the solvent, a contacting temperature comprised from from 80 to 1 15 °C and a contacting time comprise from 30 to 90 s.
- the solution containing the activated reagents is directly sprayed into the spray-dryer, whereby the dry MOF crystals are obtained at mild conditions and short time (step b in the process of the invention).
- the reaction temperature of step b), that is, inside the spray dryer can be comprised from 80 and 200 °C, more particularly between 100 and 180 °C, and still more particularly between 120 and 180 °C.
- the reaction time is usually below 6 hours to obtain the dry product.
- the reaction time is between 3 minutes and 4 hours, more preferably between 5 minutes and 4 hours, more preferably between 7 minutes and 3 hours, more preferably between 8 minutes and 2 hours, more preferably between 9 minutes and 1 hour, and still more preferably between 10 minutes and 30 minutes.
- the synthesis of MOFs may benefit from the presence of a base or an acid, since the base or the acid can further reduce the reaction time and/or the reaction temperature and/or the crystallinity of the synthesized MOF.
- the base or the acid is introduced in the activation step simultaneously with the reagent solution, just before the activated reagent solution is sprayed, or simultaneously with the activated reagent solution into the spray-dryer, preferably through a different nozzle.
- the process of the invention takes place in the presence of a base or an acid.
- the base or the acid is introduced in the activation step simultaneously with the reagent solution
- any base or an acid can be used in the method of the invention.
- preferred bases or acids are selected from the group consisting of metal alkaline or earth alkaline hydroxides, amines, metal alkaline or earth alkaline carbonates, metal alkaline or earth alkaline acetates, pyridines, azoles, diazines, acetic acid, hydrochloric acid, formic acid, and mixtures thereof.
- Any regular spray dryer can be employed to produce dry crystalline MOFs according to the invention. Preferably, large industrial spray dryers are used.
- Such industrial spray dryers can produce very large quantities of MOFs according to the present method in surprisingly short times.
- the spray dryer must have as many nozzles as are required for the spraying of the reactants, solvents and, sometimes, the base or the acid.
- air is employed as the hot gas stream, however, other gases can be employed, such as nitrogen.
- Industrial spray dryers have large capacity drums for product collection.
- the spray dryer drum is coupled to a powder-removing device.
- the device removes the formed MOF powder at regular intervals, making place for newly synthesized MOF, such that the production must not be regularly stopped to empty the drum.
- the device for performing the contacting step is coupled to the spray dryer such that the process need not be discontinued before spray-drying.
- the contacting step takes place inside a heated coil flow reactor which is coupled to the spray dryer.
- this purification step comprises washing the MOF crystals with an appropriate solvent and drying.
- This purification step is also known as "extraction step” because it removes the solvent or other molecules that are retained in MOF pores. By washing the porous material with an appropriate solvent, the new solvent molecules replace whatever molecules had remained in the pores and are subsequently removed by a gentle evaporation process.
- the solvent used for extraction can be identical to or different from that used for the reaction of the at least one metal ion with the at least one organic ligand which is at least bidentate.
- solvents for the purification or extraction step the following can be mentioned: water, methanol, ethanol, isopropanol, heptane, hexane, pentane, cyclohexane, alkenes, DMF, DEF, DMSO, dioxane, chloroform, dichloromethane, diethyl ether, acetonitrile, toluene, benzene, THF, chlorobenzene, ethylene glycol, and mixtures thereof.
- this purification step is not always required since the process of the invention may produce a sufficiently pure MOF.
- reaction parameters inside the spray dryer need to be optimized for each MOF product and each spray- dryer.
- reagent concentrations, choice of solvent, choice of base, gas spray flow, drying gas flow, feed flow and temperature, among others are parameters to be adjusted.
- the spray-dryer being employed may also influence process parameters.
- the skilled person knows how to adjust the general parameters in order to obtain the required product.
- any MOF can be obtained by the process of the invention.
- this process is particularly suitable for synthesis of MOFs which are based in complex and large SBUs, and which could not be prepared at all (or could not be prepared with good yields and/or good properties) by the state of the art spray-drying method.
- the process of the invention is suitable for obtaining MOFs pertaining to the series: UiO-66, MTV-UiO-66, [Ni 8 (OH) 4 (H 2 O)2(L) 6 ] n , CPO-27-M (also known as MOF-74) and MIL-100.
- MOFs require the activation step disclosed in the present application. Particular activating conditions for the preparation of some of these MOFs follow below.
- UiO-66 series Reagents ZrCI 4 , ZrOCI 2 -8H 2 O, Zr(NO 3 ) 4 or Zr(SO 4 ) 2 -4H 2 O and dicarboxylic acid.
- ZrCI 4, ZrOCI 2 -8H 2 O, Zr(NO 3 ) 4 or Zr(SO 4 ) 2 -4H 2 O from 0.05 to 1 M and ligand from 0.05 to 0.6 M, preferably ZrCI 4 and organic ligand at 0.1 M.
- Solvent DMF and H 2 O, preferably DMF:H 2 O from 11 .5:1 to 1 7.5: 1 , preferably 12.9:1 .
- proportion (ratio) in which each solvent is present in the solvent mixture is expressed as
- Temperature 105-120 °C, preferably 1 10-120 °C, preferably 1 15 °C.
- Contacting time 30-70 s, preferably 63 s.
- Ni(CH 3 COO) 2 -4H 2 O or Ni(NO 3 ) 2 -6H 2 O and 1 H-pyrazole-4- carboxylic acid Preferably: Ni(CH 3 COO) 2 -4H 2 O or Ni(NO 3 ) 2 -6H 2 O from 0.01 to 0.1 M and 1 H-pyrazole-4-carboxylic acid from 0.01 to 0.1 M; in particular Ni(CH 3 COO) 2 -4H 2 O at 0.02 M and 1 H-pyrazole-4-carboxylic acid at 0.015 M; Solvent: DMF and H 2 O; preferably DMF:H 2 O from 1 :1 to 5.6:1 , preferably 4:1 Temperature: 90-1 10 °C, preferably 95-105 °C, preferably 100 °C
- Contacting time 30-70 s, preferably 63 s.
- M(CH 3 COO) 2 (M Zn(ll), Co(ll), Ni(ll)) or Cu(NO 3 ) 2 2.5H 2 O from 0.1 M to 0.8 M and dihydroxy-1 ,4- benzenedicarboxylic acid from 0.05 M to 0.5 M; in particular metal salt at 0.2 M and Dihydroxy-1 ,4-benzenedicarboxylic at 0.1 M.
- MTV-UiO-66 series Reagents ZrCI 4 , ZrOCI 2 -8H 2 O, Zr(NO 3 ) 4 or Zr(SO 4 ) 2 -4H 2 O and dicarboxylic acid.
- ZrCI 4 , ZrOCI 2 -8H 2 O, Zr(NO 3 ) 4 or Zr(SO 4 ) 2 -4H 2 O from 0.05 to 1 M and dicarboxylic ligand from 0.05 to 0.6 M, in particular ZrCI 4 and organic ligand at 0.1 M.
- Solvent DMF and H 2 O, preferably DMF:H 2 O from 11 .5:1 to 17.5:1 , preferably 12.9:1 .
- Temperature 105-120 °C, preferably 1 10-120 °C, preferably 1 15 °C.
- Contacting time 30-70 s, preferably 63 s.
- Fe(NO 3 ) 3 , FeCI 3 , or Fe 3 O(OAc) 6 CIO 4 and benzene-1 ,3,5- tricarboxylic acid Preferably: Fe(NO 3 ) 3 , FeCI 3 or Fe 3 O(OAc) 6 CIO 4 from 0.05 to 1 M and benzene-1 ,3, 5-tricarboxylic acid from 0.05 to 0.6 M, in particular Fe(NO 3 ) 3 at 0.1 M and benzene-1 ,3, 5-tricarboxylic acid at 0.07 M.
- Contacting time 30-90 s, preferably 63 s.
- the MOFs obtained by the process of the invention may be in the form of spherical beads of size comprised from 0.1 to 100 ⁇ . These beads possess surprisingly high MOF particle density. It is possible to tune the size of the obtained MOF beads to meet the requirements of their industrial application by varying some parameters of the spray drying process, in particular by varying the nozzle diameter in the spray dryer. Thus, for example, MOF beads of relatively bigger size (30-400 ⁇ ) that have no need of further shaping may be produced for gas storage applications. Alternatively, smaller beads (0.1 -30) ⁇ may be provided for chromatographic applications.
- the spherical MOF beads of the invention have a size comprised from 0.5 to 100 ⁇ , or from 0.1 to 10 ⁇ , or from 0.5 to 50 ⁇ , or from 1 to 100 ⁇ , or from 1 to 50 ⁇ .
- the resulting mixture was pumped at a feed rate of 2.4 mL-min "1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C.
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected.
- the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
- the figure 3 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-1 ,4-BDC-Br compared with the simulated pattern of the bare UiO- 66 reported in the literature (Cavka S. S. Y, et al, supra). The patterns are identical, which demonstrates that the present process produced the same MOF. 1.4. Preparation of a Zr-2,5-dihydroxy-1 ,4-benzenedicarboxylic acid MOF (Zr-1 ,4-BDC-(OH) 2 )
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
- Zr-NDC Zr-2,6-Naphthalenedicarboxylic Acid MOF
- the resulting mixture was pumped at a feed rate of 2.4 mL-min "1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C.
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected.
- the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
- the figure 5 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-NDC and the simulated XRPD of the MOF (also known as MIL- 140-B) reported by Guillerm et al (Guillerm, V., Ragon, F., Dan-Hardi, M., Devic, T., Vishnuvarthan, M., Campo, B., Vimont, A., Clet, G., Yang, Q., Maurin, G., Ferey, G., Vittadini, A., Gross, S. and Serre, C.
- XRPD X-ray powder diffraction
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected. Then, the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
- the figure 6 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-1 ,4-BDC-NO 2 compared with the simulated pattern of the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, supra).
- the patterns are identical, which demonstrates that the present process produced the same MOF.
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two- fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole- size. After 6 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected. Then, the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
- the figure 8 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-1 ,4-NDC compared with the simulated pattern of the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, supra).
- the patterns are identical, which demonstrates that the present process produced the same MOF.
- the figure 9 shows the X-ray powder diffraction (XRPD) pattern of the obtained MOF, which gave diffraction peaks matching those of the simulated pattern of [Ni 8 (OH) 4 (H 2 O) 2 (L) 6 ] n obtained by the method reported in the literature (Padial, N. M., E. Quartapelle Procopio, C. Montoro, E. Lopez, J. E. Oltra, V. Colombo, A. Maspero, N. Masciocchi, S. Galli, I. Senkovska, S.
- XRPD X-ray powder diffraction
- the resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 nriL-min " using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This process was repeated twice with ethanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum.
- the pre-heated solution was spray dried on the Mini Spray Dryer B- 290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 /h, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes an orange powder was collected. Then, the orange powder was dispersed in 50 mL of H 2 O at 100 °C under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol at 70 °C. The final product was dried for 12 h at 70 °C under vacuum.
- the yield was 0.25 g (78 % w/w).
- the specific surface area (BET method) was 1039 m 2 -g "1 .
- the X-ray powder diffraction (XRPD) pattern (figure 14) of the MOF confirms that the solid obtained by the present process is comparable to that commercially available Basolite F300.
- the resulting pre-heated solution was then spray-dried at a T 2 of 180 °C and a flow rate of 336 mL-min " 1 using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This process was repeated twice with methanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum.
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice. Then, the powder was dispersed in 15 mL of methanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated three times. The final product was dried for 12 h at 80 °C under vacuum.
- the figure 16 shows the X-ray powder diffraction (XRPD) pattern of the obtained MOF (also known as CPO-27-Co) compared with the simulated pattern of the CPO-27-Co reported in the literature (Dietzel, P. D. C, Morita, Y., Blom, R., & Fjellvag, H. "An In Situ High-Temperature Single-Crystal
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes a brown powder was collected. Then, the brown powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice. Then, the powder was dispersed in 15 mL of methanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated three times. The final product was dried for 12 h at 80 °C under vacuum.
- the figure 17 shows the X-ray powder diffraction (XRPD) pattern of the obtained MOF, which gave diffraction peaks matching those of the simulated pattern of CPO-27-Ni obtained by solvothermal method reported in the literature (Dietzel, P. D. C, Panella, B., Hirscher, M., Blom, R., & Fjellvag, H. "Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework", Chemical Communications 2006, (9), 959-959), which demonstrates that the present process produced the same MOF. 5.4.
- XRPD X-ray powder diffraction
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 -h "1 , inlet air temperature of 180 °C, outlet air temperature of
- the pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 /h, inlet air temperature of 150 °C, outlet air temperature of 100 °C, and with a spray cap with 0.5 mm-hole-size. After 10 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of Ethanol and then precipitated by centrifugation. This process was repeated three times. Then, the powder was dispersed in 15 mL of Ethanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated once with 15 mL of acetone. The final product was dried for 12 h at 80 °C.
- the crystallinity and the phase purity were confirmed by PXRD (figure 20), showing that the Zr-1 ,4-BDC-NH 2 (UiO-66-NH 2 ) is isostructural with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra).
- the figure 20 shows Scanning Electron Microscopy (SEM) image for the material, revealing the formation of spherical superstructures created by the close packing of nanoparticles.
- the pre-heated solution was spray dried on the Mini Spray Dryer B- 290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m 3 /h, inlet air temperature of 140 °C, outlet air temperature of 100 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes a white powder was collected. Then, the white powder was dispersed in 40 mL of water at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 40 mL of ethanol. The final product was dried for 12 h at 80 °C.
- the figure 21 shows the scanning Electron Microscopy (SEM) image of the spherical superstructure of zirconium fumarate and their X-ray powder diffraction (XRPD) pattern, which gave diffraction peaks matching those of the simulated pattern of MOF-801 obtained by solvothermal method reported in the literature (H. Furukawa, F.Gandara, Y-B. Zhang, J. Jiang, W. Queen, M. Hudson, and O. Yaghi "Water Adsorption in Porous Metal-Organic Frameworks and Related Materials", Journal of the American Chemical Society, 2014, 136(1 1 ), 4369-4381 ), which demonstrates that the present process produced the same MOF.
- SEM scanning Electron Microscopy
- EP1373277 EP2764004 Cavka, J. H., Jakobsen, S., Olsbye, U., Guillou, N., Lamberti, C, Bordiga, S., & Lillerud, K. P. "A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability", Journal of the American Chemical Society, 2008, 130(42), 13850-13851 . Guillerm, V., Ragon, F., Dan-Hardi, M., Devic, T., Vishnuvarthan, M., Campo, B., Vimont, A., Clet, G., Yang, Q., Maurin, G., Ferey, G., Vittadini, A., Gross, S. and Serre, C. "A series of isoreticular, highly stable, porous zirconium oxide based metal-organic frameworks", Angewandte Chemie, International Edition, 2012, 51 (37), 9267-9271 .
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Abstract
The present application refers to a process for the preparation of dry crystalline metal organic frameworks which comprises: a) contacting at least one metal ion and at least one organic ligand which is at least bidentate in the presence of a solvent at a temperature comprised from 70 °C to 150 °C during a time comprised from 20 to 110 s, b) spray drying the mixture obtained from step a) under conditions appropriate to form dry crystalline metal organic frameworks, and c) collecting the formed dry crystalline metal organic frameworks. Also provided are crystalline metal organic frameworks obtained by this process.
Description
METHOD FOR THE PREPARATION OF METAL ORGANIC FRAMEWORKS
This application claims the benefit of European Patent Application
EP16382120.0 filed March 18, 2016.
FIELD OF THE INVENTION
The present invention is related to the field of material chemistry, particularly, metal organic chemistry. The invention provides a method for the industrial preparation of metal organic frameworks.
BACKGROUND ART
Metal organic frameworks, also termed MOFs, form an interesting class of microporous or mesoporous substances having characteristics which allow their use in many technical fields, such as storage, separation or controlled release of chemical substances, catalysis and drug delivery. These potential applications are a direct consequence of the porous architecture of MOFs, which leads to high specific surface area of these materials.
MOFs are composed of two major components: a metal ion or cluster of metal ions and an organic molecule that plays the role of a ligand. The organic units are typically di-, tri- or polydentate ligands. The choice of metal and organic ligand has significant effects on the structure and properties of the MOF. For example, the metal coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal and in which orientation.
MOFs are produced almost exclusively by hydrothermal or solvothermal techniques, where crystals are slowly grown from a hot solution of metal precursor, such as metal salts, and bridging ligands. Since ligands in MOFs typically bind reversibly, the usual slow growth of crystals allows defects to be redissolved, resulting in a material with milli- and micrometer-scale crystals and a near-equilibrium defect density.
As a result of their industrial applicability, preparation of porous MOFs has attracted an interest over the last years, with numerous strategies having
been described in the literature. For instance, WO2010058123 and EP1070 538 disclose methods for hydrothermal preparation of MOFs. Similarly, US20100076220 discloses a process for the obtaining of crystalline porous metal organic compounds in a liquid phase at elevated temperature.
However, the use of MOFs for industrial applications, such as storage materials for consumer products, demands an immense scale-up of their synthesis. Most of the available methodologies imply the use of high temperatures, high pressure and long crystallization times. The required conditions thus obstruct considerably the scale-up of MOF preparation which is required for industrial application.
A scaled-up process using mild conditions has been disclosed in
US20090042000. This patent application discloses the preparation of kilogram quantities of Cu-benzene-1 ,3,5-tricarboxylic acid (1 ,3,5-BTC) by reacting an admixture of a copper nitrate with 1 ,3,5-BTC in the liquid phase at atmospheric pressure above 80 °C. Still, long crystallization times between 15 and 96 hours are needed to obtain the crystalline MOF. Shorter reaction times with mild conditions are disclosed in EP1373277. This document describes a method for the hydrothermal preparation of zinc terephtalate framework with good yields, the method comprising the reaction of an admixture of a zinc salt with terephtalic acid. The method requires the presence of a base (triethylamine) and a lactam or a lactone solvent.
However, even though the reaction time is shortened with respect to other methods, at least 3 hours of continuous stirring are needed to obtain a small quantity of MOF product, and no scale up has been attempted.
Additionally, most known preparation processes require the obtained MOF crystal to be separated from the mother liquor and further dried to obtain the final MOF product. The separation and drying steps add up to the already long preparation times.
Very recently, EP2764004 disclosed large-scale MOF production at mild conditions and good yields. Said process comprises spray drying a metal ion and an organic ligand which is at least bidentate into a spray dryer in the presence of a solvent. Reaction times needed for the synthesis of MOFs are
thereby greatly reduced and dry crystalline MOFs, such as HKUST-1 and other Cu-based MOFs, are provided directly out of the initial liquid reagents (without the need of filtering and drying). Despite this being a huge advance in the field, many interesting MOF subfamilies cannot be obtained with good yields and/or good properties by this method. Important MOFs like the UiO- 66, CPO-27-M subfamilies, among others, must still be prepared by
conventional hydrothermal methodologies, which carry all the disadvantages mentioned above. Thus, even though considerable improvements have been made in the preparation of MOFs at industrial conditions, there is still the need to provide methods that are suitable for the large-scale industrial preparation of a wide variety of MOFs. SUMMARY OF THE INVENTION
The inventors have developed an alternative spray-drying process which allows for rapid, large-scale production at mild conditions of a wide variety of MOFs, some of which could not be obtained at these advatageous conditions by prior art methods, or were obtained with low yields and/or poor quality. The new method comprises first subjecting the reagents to a short activating step before spray-drying the activated reagents to form the dry, crystaline MOF.
Thus the first aspect of the invention relates to a process for the preparation of dry crystalline metal organic frameworks which comprises:
a) contacting at least one metal ion and at least one organic ligand which is at least bidentate in the presence of a solvent at a temperature comprised from 70 °C to 150 °C during a time comprised from 20 to 1 10 s,
b) spray drying the mixture obtained from step a) under conditions
appropriate to form dry crystalline metal organic frameworks, and
c) collecting the formed dry crystalline metal organic frameworks.
Figure 19 shows a schematic representation of a particular embodiment of the method of the invention. During step a) the reagents are activated forming Secondary Building Units (SBU) which are more suitable starting points for synthesis of different types of MOF which are based in complex and large SBUs, such as oxoclusters in the case of UiO-66 series or helical rods in the
CPO-27 family, opening the way to mass production of these industrially relevant materials. Selecting the optimal combination of conditions at which appropriate activation of the reagents is achieved is crucial for obtaining good quality MOF at high yields. Sub-optimal conditions will either not achieve formation of the required SBU or will promote growth of the MOF crystal thus interfering with the spray-drying of the (over-) activated solution (step b). Over-activation during step a) may stopple the spray-dryer's noozle, reduce the yield and/or result in poor quality MOF. Under-activation will result in poor quality MOF and/or a poor yield, or even no MOF at all.
Advantageously, the activation and spray-drying (steps a and b in the first aspect of the invention) may be performed in continuous flow. The whole process may be continuous by installing a continuous unloading system for collecting the dry crystalline MOF (step c).
The process of the invention of course has all the advantages described for the prior spray-drying method: mild conditions, regular industrial equipment, drastically reduced reaction times and reduced dimensions of the obtained MOFs. Altogether, the process is scalable, clean, economical and
environmental friendly.
In addition to producing MOF families which could not be obtained with the prior spray-drying method, the present process has the advantage of improving crystallinity of MOF particles. Further, the obtained MOFs are usually in the form of spherical beads of size comprised from 0.1 to 400 μιτι.
Such beads are compact tiny particles, highly robust and difficult to break which cannot be obtained by means previously disclosed. The resulting product has the advantage of possessing surprisingly high MOF particle density, in addition to intrinsically high specific surface area, which translates into higher absorption capacity when compared to prior art products. While having such high MOF density, the product of the invention is also
advantageous in terms of storing and transportation.
Thus a second aspect of the invention refers to crystalline metal organic frameworks obtained by the process as defined above. Such MOFs are preferably in the form of spherical beads, usually of size comprised from 0.1 to 400 pm.
The crystals directly obtained by the process of the invention may have purity up to 99% (w/w). Additional washing and drying steps result in substantially pure crystals. Altogether, the process of the invention contributes to MOF quality and increases production ease and yield.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 : a) X-ray powder diffraction (XRPD) pattern of Zr-1 ,4-BDC (also known as UiO-66) obtained according to the invention (upper pattern) and simulated pattern of UiO-66 obtained by solvothermal method reported in the literature (Cavka S. S. Y. et al) (lower pattern), b) Scanning Electron Microscopy (SEM) image of the spherical superstructure of Zr-1 ,4-BDC of the invention. FIG 2: a) XRPD pattern of Zr-1 ,4-BDC-NH2 (UiO-66-NH2) obtained according to the invention ( example 1 .2) (upper pattern) and bare UiO-66 reported in the literature (Cavka S. S. Y., et al, lower pattern), b) SEM image for the Zr- 1 ,4-BDC-NH2 obtained according to the invention (example 1 .2). FIG 3: a) XRPD pattern of the Zr-1 ,4-BDC-Br (also known as UiO-66-Br) obtained according to the invention (upper pattern) and bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image for the Zr- 1 ,4-BDC-Br obtained according to the invention. FIG 4: a) XRPD pattern of the UiO-66-(OH)2 obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, lower pattern), b) SEM image of the UiO-66- (OH)2 obtained according to the invention. FIG 5: a) XRPD pattern of the Zr-NDC obtained according to the invention
(upper pattern) compared with the MOF (also known as MIL-140-B) reported in the literature reported by Guillerm et al. b) SEM image of the Zr-NDC obtained according to the invention. FIG 6: a) XRPD pattern of UiO-66-NO2 obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-NO2
obtained according to the invention.
FIG. 7: a) XRPD pattern of Zr-1 ,4-BDC-Acetamido (UiO-66-Acetamido) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-Acetamido obtained according to the invention.
FIG. 8: a) XRPD pattern of Zr-1 ,4-NDC (UiO-66-1 ,4-NDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO- 66-1 ,4-NDC obtained according to the invention.
FIG. 9: a) XRPD pattern of [Ni8(OH)4(H2O)2(L)6]n obtained according to the invention (upper pattern) compared with the bare [Ni8(OH)4(H2O)2(L)6]n reported in the literature (Padial, et al, lower pattern), b) SEM image of the [Ni8(OH)4(H2O)2(L)6]n obtained according to the invention
FIG. 10: a) XRPD pattern of UiO-66-(BDC-Br)0 5(BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66- (BDC-Br)0 5(BDC) obtained according to the invention.
FIG. 11 : a) XRPD pattern of UiO-66-(BDC-Br)(BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-
(BDC-Br)(BDC) obtained according to the invention.
FIG. 12: a) XRPD pattern of UiO-66-(BDC-Br)2(BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-
(BDC-Br)2(BDC) obtained according to the invention.
FIG. 13: a) XRPD pattern of UiO-66-(BDC-Br)(BDC)(NH2-BDC) obtained according to the invention (upper pattern) compared with the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, lower pattern), b) SEM image of the UiO-66-(BDC-Br)(BDC)(NH2-BDC) obtained according to the invention.
FIG. 14: a) XRPD pattern of Fe-1 ,3,5-BTC obtained according to the invention (upper pattern) compared with the simulated powder pattern for Fe-1 ,3,5- BTC. b) SEM image of the Fe-1 ,3,5-BTC obtained according to the invention. FIG. 15: a) XRPD pattern of CPO-27-Zn obtained according to the invention (upper pattern) compared to the CPO-27-Zn synthesized by the solvothermal method reported in the literature (Rosi N. L, et al, lower pattern), b) SEM image of the CPO-27-Zn obtained according to the invention. FIG. 16: a) XRPD pattern of CPO-27-Co obtained according to the invention (upper pattern) compared to the CPO-27-Co reported in the literature
(Dietzel, P. D. C, et al, 2005, lower pattern), b) SEM image of the CPO-27-Co obtained according to the invention. FIG. 17: a) XRPD pattern of CPO-27-Ni obtained according to the invention (upper pattern) compared to the CPO-27-Ni reported in the literature (Dietzel, P. D. C, et al, 2006, lower pattern), b) SEM image of the CPO-27-Ni obtained according to the invention. FIG. 18: a) XRPD pattern of CPO-27-Cu obtained according to the invention (upper pattern) compared to the CPO-27-Zn synthesized by the solvothermal method reported in the literature (Rosi N. L, et al, lower pattern), b) SEM image of the CPO-27-Zn obtained according to the invention. FIG. 19: Schematic representation of the synthesis of a MOF UiO-66 according to the invention. Δ, activation; SD, spray srying; 1 , reagents; 2, secondary building unit; 3, UiO-66 crystal.
FIG 20: a) XRPD pattern of Zr-1 ,4-BDC-NH2 (UiO-66-NH2) obtained according to the invention (example 6) (upper pattern) and bare UiO-66 reported in the literature (Cavka S. S. Y., et al, lower pattern), b) SEM image for the Zr-1 ,4-BDC-NH2 obtained according to the invention (example 6).
FIG 21 : a) XRPD pattern of MOF-801 obtained according to the invention (example 7) (upper pattern) and bare MOF-801 reported in the literature (Furukawa H, et al, lower pattern), b) SEM image for the MOF-801 obtained according to the invention (example 7).
DETAILED DESCRIPTION OF THE INVENTION
The invention is related to a facile, rapid and scalable method for the synthesis of MOFs, including complex MOFs, in a continuous flow reactor coupled to the spray dryer, combining the benefits of both systems as efficient mass and heat transfer during the continuous flow zone (activation step) and the possibility to confine the synthesis in individual reactors (atomized droplets) for the assembly of the MOF (growth step).
"Metal Organic Frameworks", also termed MOFs, are crystalline compounds consisting of metal ions coordinated to often rigid organic molecules to form one-, two-, or three-dimensional structures that are highly porous. By "organic ligand which is at least bidentate" it is understood an organic compound that is able to bind at least two metal ions through coordination bonds.
The term "spraying" (also known as atomizing) refers to the process of forming a spray, which is a dynamic collection of drops dispersed in a gas.
A "spray dryer" is a device well known in the state of the art where a liquid input stream is sprayed in small droplets through a nozzle (or atomizer) into a hot gas stream.
By "activating" in the sense of the present invention it is meant the process by which the reagents form Secondary Building Units (SBUs). "SBUs" are molecular complexes and cluster entities in which ligand coordination modules and metal coordination environments can be utilized in the
transformation of these fragments into extended porous frameworks (i.e.
MOFs).
The MOFs obtained by the process of the invention are usually in the form of tiny spherical beads with surprisingly high MOF density which translates in surprisingly high absorption capacity. The size of these beads is usually from 0.1 to 400 pm.
By "spherical beads" it is meant particles of spherical or quasi-spherical morphology. The beads are thus not necessarily perfect spheres but may be substantially spherical particles, i.e. comparable to a sphere. The term "bead" in the context of the present invention further implies that the particles are stuffed, i.e. they are not empty capsules but sound compact particles entirely formed by MOFs. Obtaining such high density MOF beads by a rapid, clean scalable and economical process has not been previously described.
As used herein, the term "size" refers to a characteristic physical dimension. For example, in the most usual case of a microcapsule that is spherical or substantially spherical, the size of the microcapsule corresponds to the diameter of the sphere or the equivalent diameter of the quasi-sphere assimilated as a sphere. The state of the art provides appropriate techniques and equipments to calculate the diameter of particles and in particular of spheres or substantially spherical particles. For example, the diameter can be measured using laser diffraction analysis. Alternatively, the size (diameter) of the beads of the invention may be calculated from their images, for example from SEM images, by hand or applying an appropriate imaging software such as Gatan microscopy suite software. When referring to a set of spherical beads as being of a particular size, it is contemplated that the set of beads can have a distribution of sizes around the specified size. Thus, as used herein, a size of a set of beads can refer to a mode of a distribution of sizes, such as a peak size of the distribution of sizes. As mentioned above, optimal conditions for the activating step are required to efficiently form SBUs that enable further synthesis of MOFs by spray-drying. In some embodiments, conditions in the activating step a) of the process of the invention are contacting at least one metal ion and at least one organic ligand which is at least bidentate in the presence of a solvent at a
temperature comprised from 80 °C to 150 °C during a time comprised from 20 to 100 s.
In particular embodiments the contacting temperature is comprised from 70 to 150 °C, or from 80 to 140 °C, or from 90 to 130 °C, or from 90 to 120 °C, or from 100 to 125 °C or from 100 to 120 °C, or from 100 to 1 15 °C, or from 1 10 to 120 °C, or from 80 to 1 15 °C, or from 80 to 1 10 °C, or from 90 to 1 10 °C, or from 85 to 105 °C, or from 80 to 100 °C, or from 90 to 100 °C.
In further particular embodiments the contacting step is performed during a time comprised from 20 to 1 10 s, or from 30 to 90 s, or from 40 to 80 s, or from 50 to 90 s, or from 50 to 70 s, or from 40 to 50 s, or from 50 to 60 s, or from 60 to 70 s, or from 70 to 80 s.
The metal ions for use in the process of the invention are those usually employed for the preparation of MOFs. Non-limiting metal ions are those from chemical elements in the following groups: alkali metals (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), transition metals (Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg) and post-transition metals (Al, Ga, In, TI, Sn, Pb, Bi), as well as metalloids (B, Si, Ge, As, Sb, Te, Po), lanthanides (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and actinides (Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr). Unusual metals not mentioned above or newly discovered could be also used in the method of the invention. In one embodiment the at least one metal ion is selected from the group consisting of Zr, Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Zr, Gd, Eu, Tb, and mixtures thereof. In a preferred embodiment the at least one metal ion is selected from the group consisting of Zr, Zn, Cu, Fe, Gd, Mg, and mixtures thereof.
Practically speaking, the metal ion is provided as a compound which is a source of a metal ion, usually a salt. Non-limiting examples of metal salts for use in the invention are nitrates, chlorides, sulphates, acetates, hydroxides, oxides, acetylacetonates, bromides, carbonates, carboxylates, tartrates and perchlorates.
In certain embodiments, MOF formation can take place by reacting more than one metal ion. In one embodiment the process of the invention is performed by reacting between one and six different metal ions. In a preferred
embodiment the process of the invention is performed by reacting between one and three different metal ions. In a more preferred embodiment the process of the invention is performed by reacting between one and two different metal ions. For example, the MOF can be synthesized by reacting two metal ions with at least one organic ligand which is at least bidentate according to the present invention.
According to the invention it is also possible that the MOF is formed by the reaction of one or more metal ions with one or more organic ligands. In one embodiment the process of the invention is performed by reacting between one and six organic ligands which are at least bidentate. In a preferred embodiment the process of the invention is performed by reacting from one to three organic ligands which are at least bidentate. In a more preferred embodiment the process of the invention is performed by reacting from one to two organic ligands which are at least bidentate.
Thus, the metal ion or ions coordinate with one or more organic compounds that act like a ligand. The organic ligands in the sense of the present invention must be at least bidentate, meaning that they must be able to bind at least two metal ions by coordination bonds. The organic ligands according to the invention can be bidentate, but also tridentate, tetradentate or pluridentate in the sense that they may coordinate two, three, four or multiple metal ions through coordination bonds. In one embodiment, the organic ligand coordinates between 2 and 20 metal ions. In a preferred embodiment, the organic ligand coordinates between 2 and 12 metal ions. In a more preferred embodiment, the organic ligand coordinates between 2 and 8 metal ions. The ability to coordinate metal ions is conferred by certain functional groups. Non-limiting functional groups that can be contained by the organic ligand to form a MOF according to the invention are -COOH, -CSSH, -NO2, - B(OH)2, -SO3H, -Ge(OH)3, -Sn(OH)3, -Si(SH)4, -Ge(SH)4, -Sn(SH)3, -PO3H, - AsOsH, -AsO4H, -P(SH)3, As(SH)3, C4H2O4, -RSH, -RNH2, -RNR-, -ROH, -
RCN, -PO(OR)2, -RN3, where R is hydrogen, alkyl, alkylene, preferably C1 , C2, C3, C4 or C5 alkylene, or aryl group, preferably comprising 1 or 2 aromatic nuclei. In one embodiment, the at least one organic ligand which is at least bidentate contains functional groups selected from the group consisting of a
carboxylate, a phosphonate, an amine, an azide, a cyanide, a squaryl, an heteroatom, and mixtures thereof. Preferred heterocycles contain O, S and/or N. Non-limiting examples of preferred heterocycles in the sense of the invention are azoles, pyridines and diazines.
The at least one organic ligand which is at least bidentate may be comprised
of at least one functional group as mentioned above bound to any suitable organic compound, provided that it is ensured that the organic ligand is capable of coordinating at least two metal ions. In another embodiment, the at least one organic ligand which is at least bidentate is a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, imidazole, or mixtures thereof.
In a preferred embodiment, the at least one organic ligand which is at least bidentate is selected from the group consisting of formic acid, acetic acid, oxalic acid, propanoic acid, butanedioic acid, (E)-butenedioic acid, benzene- 1 ,4-dicarboxylic acid, benzene-1 ,3-dicarboxylic acid, benzene-1 ,3,5- tricarboxylic acid, 2-amino-1 ,4-benzenedicarboxylic acid, 2-bromo-1 ,4- benzenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, biphenyl-3,3',5,5'- tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, 2,5-dihydroxy-1 ,4- benzenedicarboxylic acid, 1 ,3,5-tris(4-carboxyphenyl)benzene, (2E,4E)-hexa- 2,4-dienedioic acid, 1 ,4-naphthalenedicarboxylic acid, naphthalene-2,6- dicarboxylate, pyrene- 2,7-dicarboxylic acid, 4,5,9,10-tetrahydropyrene-2, 7- dicarboxylic acid, aspartic acid, glutamic acid, adenine, 4,4'-bypiridine, pyrimidine, pyrazine, 1 ,4-diazabicyclo[2.2.2]octane, pyridine-4-carboxylic acid, pyridine-3-carboxylic acid, imidazole, 1 /-/-benzimidazole, 2-methyl-1 H- imidazole, 4-methyl-5-imidazolecarboxaldehyde, 1 H-pyrazole-4-carboxylic acid, dihydroxy-1 ,4-benzenedicarboxylic acid, benzene-1 ,3, 5-tricarboxylic acid, 2-Acetamido-1 ,4-benzenedicarboxylic acid, 2-Nitro-1 ,4- benzenedicarboxylic acid .
In another embodiment, the at least organic ligand which is at least bidentate is a peptide. The process of the invention requires that a solvent is present for the reagents to form the MOF. The term "solvent" relates to individual solvents and also to mixtures of different solvents. The solvent can be any aqueous or non-aqueous solvent. In certain embodiments of the invention, mixtures of two or more solvents are used. In a particular embodiment, the solvent is selected from the group consisting of water, (C1 -C6)-alcohols, (C5-C7)- alkanes, alkenes, (C3-C8)-cycloalkanes, N, A/-di methyl formamide (DMF), Λ/,/V-diethyl formamide (DEF), dimethyl sulfoxide (DMSO), dioxane,
chloroform, dichloromethane, diethyl ether, acetonitrile, toluene, benzene, tetrahydrofuran (THF), chlorobenzene, ethylene glycol, and mixtures thereof. Preferred alcohols are methanol, ethanol and isopropanol. Preferred alkanes are hexane, heptane and pentane. In a preferred embodiment the solvent is selected from water, ethanol, DMF and mixtures thereof.
In particular embodiments of the invention, the conditions for the activation step comprise water as the solvent, a contacting temperature comprised from from 80 to 1 15 °C and a contacting time comprise from 30 to 90 s. In other particular embodiments of the invention, the conditions for the activation step comprise water as the solvent, a contacting temperature comprised from from 80 to 100 °C and a contacting time comprise from 30 to 90 s. In another particular embodiment, the conditions for the activation step comprise ethanol as the solvent, a contacting temperature comprised from from 80 to 1 15 °C and a contacting time comprise from 30 to 90 s. In another particular embodiment, the conditions for the activation step comprise a mixture of water and ethanol as the solvent, a contacting temperature comprised from from 80 to 1 15 °C and a contacting time comprise from 30 to 90 s. After the activation step, the solution containing the activated reagents is directly sprayed into the spray-dryer, whereby the dry MOF crystals are obtained at mild conditions and short time (step b in the process of the invention). The reaction temperature of step b), that is, inside the spray dryer, can be comprised from 80 and 200 °C, more particularly between 100 and 180 °C, and still more particularly between 120 and 180 °C.
The reaction time is usually below 6 hours to obtain the dry product.
Preferably, the reaction time is between 3 minutes and 4 hours, more preferably between 5 minutes and 4 hours, more preferably between 7 minutes and 3 hours, more preferably between 8 minutes and 2 hours, more preferably between 9 minutes and 1 hour, and still more preferably between 10 minutes and 30 minutes.
The synthesis of MOFs may benefit from the presence of a base or an acid, since the base or the acid can further reduce the reaction time and/or the
reaction temperature and/or the crystallinity of the synthesized MOF. In the present invention the base or the acid is introduced in the activation step simultaneously with the reagent solution, just before the activated reagent solution is sprayed, or simultaneously with the activated reagent solution into the spray-dryer, preferably through a different nozzle. Thus, in one
embodiment, the process of the invention takes place in the presence of a base or an acid. In a particular embodiment the base or the acid is introduced in the activation step simultaneously with the reagent solution In principle any base or an acid can be used in the method of the invention. However, preferred bases or acids are selected from the group consisting of metal alkaline or earth alkaline hydroxides, amines, metal alkaline or earth alkaline carbonates, metal alkaline or earth alkaline acetates, pyridines, azoles, diazines, acetic acid, hydrochloric acid, formic acid, and mixtures thereof. Any regular spray dryer can be employed to produce dry crystalline MOFs according to the invention. Preferably, large industrial spray dryers are used. Such industrial spray dryers can produce very large quantities of MOFs according to the present method in surprisingly short times. The spray dryer must have as many nozzles as are required for the spraying of the reactants, solvents and, sometimes, the base or the acid. Usually, air is employed as the hot gas stream, however, other gases can be employed, such as nitrogen. Industrial spray dryers have large capacity drums for product collection.
Preferably, the spray dryer drum is coupled to a powder-removing device. The device removes the formed MOF powder at regular intervals, making place for newly synthesized MOF, such that the production must not be regularly stopped to empty the drum.
Further, different industrial devices may be employed for performing the activation step, so long as the activating conditions may be achieved inside the device. Preferably, the device for performing the contacting step is coupled to the spray dryer such that the process need not be discontinued before spray-drying. In one particular embodiment, the contacting step takes place inside a heated coil flow reactor which is coupled to the spray dryer. Altogether, the whole process of the invention, including activation, spray- drying and, optionally, the recollection of the dry-crystalline MOF, is preferably a continuous process.
The MOF crystals obtained by the process of the present invention have a high purity grade. Nevertheless it is typical for MOF products to be subjected to a purification step. Thus, in one embodiment, the process of the invention additionally comprises a purification step. Usually, this purification step comprises washing the MOF crystals with an appropriate solvent and drying. This purification step is also known as "extraction step" because it removes the solvent or other molecules that are retained in MOF pores. By washing the porous material with an appropriate solvent, the new solvent molecules replace whatever molecules had remained in the pores and are subsequently removed by a gentle evaporation process. The solvent used for extraction can be identical to or different from that used for the reaction of the at least one metal ion with the at least one organic ligand which is at least bidentate. As non-limiting suitable solvents for the purification or extraction step the following can be mentioned: water, methanol, ethanol, isopropanol, heptane, hexane, pentane, cyclohexane, alkenes, DMF, DEF, DMSO, dioxane, chloroform, dichloromethane, diethyl ether, acetonitrile, toluene, benzene, THF, chlorobenzene, ethylene glycol, and mixtures thereof. However, this purification step is not always required since the process of the invention may produce a sufficiently pure MOF.
The person skilled in the art is aware that the reaction parameters inside the spray dryer need to be optimized for each MOF product and each spray- dryer. For instance, reagent concentrations, choice of solvent, choice of base, gas spray flow, drying gas flow, feed flow and temperature, among others, are parameters to be adjusted. The spray-dryer being employed may also influence process parameters. The skilled person knows how to adjust the general parameters in order to obtain the required product.
Any MOF can be obtained by the process of the invention. However, as mentioned above, this process is particularly suitable for synthesis of MOFs which are based in complex and large SBUs, and which could not be prepared at all (or could not be prepared with good yields and/or good properties) by the state of the art spray-drying method. In particular, the process of the invention is suitable for obtaining MOFs pertaining to the series: UiO-66, MTV-UiO-66, [Ni8(OH)4(H2O)2(L)6]n, CPO-27-M (also known as MOF-74) and MIL-100. These MOFs require the activation step disclosed in the present application. Particular activating conditions for the preparation of
some of these MOFs follow below.
UiO-66 series Reagents: ZrCI4, ZrOCI2-8H2O, Zr(NO3)4 or Zr(SO4)2-4H2O and dicarboxylic acid. Preferably: ZrCI4, ZrOCI2-8H2O, Zr(NO3)4 or Zr(SO4)2-4H2O from 0.05 to 1 M and ligand from 0.05 to 0.6 M, preferably ZrCI4 and organic ligand at 0.1 M.
Solvent: DMF and H2O, preferably DMF:H2O from 11 .5:1 to 1 7.5: 1 , preferably 12.9:1 . When referring to solvent mixtures, the proportion (ratio) in which each solvent is present in the solvent mixture is expressed as
Solventl :Solvent2. For example a DMF:H2O = 12.9:1 means that for every
12.9 parts of DMF the mixture has 1 part of water.
Temperature: 105-120 °C, preferably 1 10-120 °C, preferably 1 15 °C.
Contacting time: 30-70 s, preferably 63 s.
Reagents: Ni(CH3COO)2-4H2O or Ni(NO3)2-6H2O and 1 H-pyrazole-4- carboxylic acid. Preferably: Ni(CH3COO)2-4H2O or Ni(NO3)2-6H2O from 0.01 to 0.1 M and 1 H-pyrazole-4-carboxylic acid from 0.01 to 0.1 M; in particular Ni(CH3COO)2-4H2O at 0.02 M and 1 H-pyrazole-4-carboxylic acid at 0.015 M; Solvent: DMF and H2O; preferably DMF:H2O from 1 :1 to 5.6:1 , preferably 4:1 Temperature: 90-1 10 °C, preferably 95-105 °C, preferably 100 °C
Contacting time: 30-70 s, preferably 63 s.
CPO-27-M series
Reagents: M(CH3COO)2, wherein M = Zn(ll), Co(ll), Ni(ll) and Cu(ll), or M(NO3)2, wherein M = Zn(ll), Co(ll), Ni(ll) and Cu(ll), and Dihydroxy-1 ,4- benzenedicarboxylic acid. Preferably: M(CH3COO)2 (M = Zn(ll), Co(ll), Ni(ll)) or Cu(NO3)2 2.5H2O from 0.1 M to 0.8 M and dihydroxy-1 ,4- benzenedicarboxylic acid from 0.05 M to 0.5 M; in particular metal salt at 0.2 M and Dihydroxy-1 ,4-benzenedicarboxylic at 0.1 M.
Solvent: DMF and H2O; preferably DMF:H2O from 3:1 to 1 :1 ; preferably DMF:H2O = 1 :1
Temperature: 80-100 °C, preferably 85-95 °C, preferably 90 °C
Contacting time: 30-70 s, preferably 63 s. MTV-UiO-66 series Reagents: ZrCI4, ZrOCI2-8H2O, Zr(NO3)4 or Zr(SO4)2-4H2O and dicarboxylic acid. Preferably: ZrCI4, ZrOCI2-8H2O, Zr(NO3)4 or Zr(SO4)2-4H2O from 0.05 to 1 M and dicarboxylic ligand from 0.05 to 0.6 M, in particular ZrCI4 and organic ligand at 0.1 M. Solvent: DMF and H2O, preferably DMF:H2O from 11 .5:1 to 17.5:1 , preferably 12.9:1 .
Temperature: 105-120 °C, preferably 1 10-120 °C, preferably 1 15 °C.
Contacting time: 30-70 s, preferably 63 s.
MIL-100 Reagents: Fe(NO3)3, FeCI3, or Fe3O(OAc)6CIO4 and benzene-1 ,3,5- tricarboxylic acid. Preferably: Fe(NO3)3, FeCI3 or Fe3O(OAc)6CIO4 from 0.05 to 1 M and benzene-1 ,3, 5-tricarboxylic acid from 0.05 to 0.6 M, in particular Fe(NO3)3 at 0.1 M and benzene-1 ,3, 5-tricarboxylic acid at 0.07 M.
Solvent: DMF
Temperature: 1 10-140 °C, preferably 135 °C
Contacting time: 30-90 s, preferably 63 s.
As shown in the figures 1 to 18, the MOFs obtained by the process of the invention may be in the form of spherical beads of size comprised from 0.1 to 100 μιτι. These beads possess surprisingly high MOF particle density. It is possible to tune the size of the obtained MOF beads to meet the requirements of their industrial application by varying some parameters of the spray drying process, in particular by varying the nozzle diameter in the spray dryer. Thus, for example, MOF beads of relatively bigger size (30-400 μιτι) that have no need of further shaping may be produced for gas storage applications. Alternatively, smaller beads (0.1 -30) μιτι may be provided for chromatographic applications. In certain embodiments, the spherical MOF beads of the invention have a size comprised from 0.5 to 100 μιτι, or from 0.1 to 10 μιτι, or from 0.5 to 50 μιτι, or from 1 to 100 μιτι, or from 1 to 50 μιτι.
Throughout the description and claims the word "comprise" and variations of the word, are not intended to exclude other technical features, additives,
components, or steps. Furthermore, the word "comprise" encompasses the case of "consisting of. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention. The following examples and drawings are provided by way of illustration, and they are not intended to be limiting of the present invention. Furthermore, the present invention covers all possible combinations of particular and preferred embodiments described herein. EXAMPLES
1. Spray-drying continuous flow-assisted synthesis of UiO-66 series.
In a typical synthesis, a solution 0.1 of ZrCI4 and 0.1 M of organic ligand in 15 ml_ of a mixture of DMF and H2O (5.48:1 ) was injected into a coil flow reactor (Pyrex tube, inner diameter: 3 mm) at a feed rate of 2.4 mL-min"1 and at a T-, of 115 °C. The resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 mL-min"1 using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This process was repeated twice with ethanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum. Characterisation
X-ray powder diffraction (XRPD) patterns were collected on an X'Pert PRO MPDP analytical diffractometer (Panalytical) at 45 kV, 40 mA using CuKa radiation (λ = 1 .5419 A). Nitrogen adsorption and desorption measurements were done at 77K using an Autosorb-IQ-AG analyser (Quantachrome
Instruments). Prior to the measurement Field-Emission Scanning Electron Microscopy (FE-SEM) images were collected on a FEI Magellan 400L scanning electron microscope at an acceleration voltage of 1 .0-2.0 Kv, using aluminium as support.
1.1. Preparation of a Zr-benzene-1 ,4-dicarboxylic acid MOF (Zr-1 ,4-BDC, also known as UiO-66)
0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 mL of a mixture of dimethylformamide (DMF, Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a solution of 0.24 g of benzene-1 ,4-dicarboxylic acid (1 ,4-BDC, Sigma-Aldrich) in 8.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected. Then, the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66: Yield = 70 %; Purity = 54 %; SBET = 1106 m2-g"1. The figure 1 shows the scanning Electron Microscopy (SEM) image of the spherical superstructure of Zr-1 ,4-BDC (also known as UiO-66) and their X- ray powder diffraction (XRPD) pattern, which gave diffraction peaks matching those of the simulated pattern of Zr-1 ,4-BDC (UiO-66) obtained by solvothermal method reported in the literature (Cavka, J. H., Jakobsen, S., Olsbye, U., Guillou, N., Lamberti, C, Bordiga, S., & Lillerud, K. P. "A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability", Journal of the American Chemical Society, 2008, 130(42), 13850-13851 ), which demonstrates that the present process produced the same MOF.
1.2. Preparation of a Zr-2-amino-1 ,4-benzenedicarboxylic acid MOF (Zr- 1 ,4-BDC "NH2J also known as U 1O-66-N H2)
A solution of 0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 mL of a mixture of DMF (Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a solution of 0.27 g 2-amino-1 ,4-benzenedicarboxylic acid (Sigma-Aldrich) in 8.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1
through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-NH2: Y\e\0 = 67 %; Purity = 49 %; SBET = 752 m2-g"1.
The crystallinity and the phase purity were confirmed by PXRD (figure 2), showing that the Zr-1 ,4-BDC-NH2 (UiO-66-NH2) is isostructural with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra). The figure 2 shows Scanning Electron Microscopy (SEM) image for the material, revealing the formation of spherical superstructures created by the close packing of nanoparticles.
1.3. Preparation of a Zr-2-bromo-1 ,4-benzenedicarboxylic acid MOF (Zr- 1 ,4-BDC-Br, also known as UiO-66-Br)
A solution of 0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 mL of a mixture of DMF (Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a solution of 0.36 g of 2-bromo-1 ,4-benzenedicarboxylic acid (Sigma-Aldrich) in 8.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 115 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected. Then, the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-Br: Yield = 68 %; Purity = 62 %; SBET = 527 m2-g"1.
The figure 3 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-1 ,4-BDC-Br compared with the simulated pattern of the bare UiO- 66 reported in the literature (Cavka S. S. Y, et al, supra). The patterns are identical, which demonstrates that the present process produced the same MOF. 1.4. Preparation of a Zr-2,5-dihydroxy-1 ,4-benzenedicarboxylic acid MOF (Zr-1 ,4-BDC-(OH)2)
0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 ml_ of a mixture of dimethylformamide (DMF, Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a solution of 0.30 g of 2,5-dihydroxy-1 ,4-benzenedicarboxylic acid (DHTP, Sigma-Aldrich) in 8.0 ml_ of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-(OH)2: Y\e\0 = 81 %; Purity = 67 %; SBET = 401 m2-g"1. The figure 4 shows Scanning Electron Microscopy (SEM) image of the obtained superstructures and their X-ray powder diffraction (XRPD) pattern compared with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra). The patterns are identical, which demonstrates that the present process produced the same MOF.
1.5. Preparation of a Zr-2,6-Naphthalenedicarboxylic Acid MOF (Zr-NDC)
A solution of 0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 mL of a mixture of DMF (Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a dispersion of 0.33 g of 2,6-naphthalenedicarboxylic acid (Sigma-Aldrich) in 8.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected. Then, the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-2,6-NDC: Y\e\0 = 49 %; Purity = 37 %; SBET = 557 m2-g"1.
The figure 5 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-NDC and the simulated XRPD of the MOF (also known as MIL- 140-B) reported by Guillerm et al (Guillerm, V., Ragon, F., Dan-Hardi, M., Devic, T., Vishnuvarthan, M., Campo, B., Vimont, A., Clet, G., Yang, Q., Maurin, G., Ferey, G., Vittadini, A., Gross, S. and Serre, C. "A series of isoreticular, highly stable, porous zirconium oxide based metal-organic frameworks", Angewandte Chemie, International Edition, 2012, 51 (37), 9267- 9271 .) demonstrate that the MOF produced by the present process is identical to that described in the literature.
1.6. Preparation of a Zr-2-nitro-1 ,4-benzenedicarboxylic acid MOF (Zr- 1 ,4-BDC-Br, also known as UiO-66-N02)
A solution of 0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 mL of a mixture of DMF (Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a solution of 0.31 g of 2-nitro-1 ,4-benzenedicarboxylic acid (Sigma-Aldrich) in 8.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 115 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland)
using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected. Then, the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-N02: Yield = 62 %; Purity = 49 %; SBET = 856 m2-g"1.
The figure 6 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-1 ,4-BDC-NO2 compared with the simulated pattern of the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, supra). The patterns are identical, which demonstrates that the present process produced the same MOF.
1.7. Preparation of a Zr-2-acetamido-1 ,4-benzenedicarboxylic acid MOF (Zr-1 ,4-BDC-Acetamido, also known as UiO-66-Acetamido) A solution of 0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 mL of a mixture of DMF
(Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a solution of 0.27 g 2-acetamido-1 ,4-benzenedicarboxylic acid in 8.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two- fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole- size. After 6 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-Acetamido: Yield = 51 %; Purity = 41 %; SBET = 586 m2-g"1
The crystallinity and the phase purity were confirmed by PXRD (figure 7), showing that the Zr-1 ,4-BDC-Acetamido (UiO-66-Acetamido) is isostructural
with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra). The figure 7 shows Scanning Electron Microscopy (SEM) image for the material, revealing the formation of spherical superstructures created by the close packing of nanoparticles.
1.8. Preparation of a Zr-1 ,4-naphthalenedicarboxylic acid MOF (Zr-1 ,4- NDC)
A solution of 0.34 g of ZrCI4 (Sigma-Aldrich) in 7.0 mL of a mixture of DMF (Fisher Scientific) and water (VDMF:Vwater - 5.48:1 ) was added to a dispersion of 0.32 g of 1 ,4-naphthalenedicarboxylic Acid (Sigma-Aldrich) in 8.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 1 15 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes a white powder was collected. Then, the white powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-1,4-NDC: Y\e\0 = 45 %; Purity = 45 %; SBET = 431 m2-g"1
The figure 8 shows the X-ray powder diffraction (XRPD) pattern of the obtained Zr-1 ,4-NDC compared with the simulated pattern of the bare UiO-66 reported in the literature (Cavka S. S. Y, et al, supra). The patterns are identical, which demonstrates that the present process produced the same MOF.
2. Spray-drying continuous flow-assisted synthesis of [Ni8(OH)4(H20)2(L)6]n.
A solution 0.02 M of Ni(CH3COO)2-4H2O and 0.015 M of 1 H-pyrazole-4- carboxylic acid in 20 mL of a mixture of DMF and H2O (4:1 ) was injected into
the coil flow reactor (Pyrex tube, inner diameter: 3 mm) at a feed rate of 2.4 mL-min"1 and at a T-i of 100 °C. The resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 mL-min"1 using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter 5 hole). Finally, the collected solid was dispersed in EtOH and precipitated by centrifugation. This two-step washing process was repeated with Et2O. The final product was dried for 12 h at 60 °C under vacuum.
Characterization of obtained MOFs was performed as described in example l o 1 .
Results for [Ni8(OH)4(H20)2(L)6]n Yield = 60 %; Purity = 81 %; SBET = 377
15 The figure 9 shows the X-ray powder diffraction (XRPD) pattern of the obtained MOF, which gave diffraction peaks matching those of the simulated pattern of [Ni8(OH)4(H2O)2(L)6]n obtained by the method reported in the literature (Padial, N. M., E. Quartapelle Procopio, C. Montoro, E. Lopez, J. E. Oltra, V. Colombo, A. Maspero, N. Masciocchi, S. Galli, I. Senkovska, S.
20 Kaskel, E. Barea and J. A. R. Navarro. "Highly Hydrophobic Isoreticular
Porous Metal-Organic Frameworks for the Capture of Harmful Volatile Organic Compounds." Angewandte Chemie International Edition (2013) 52(32): 8290-8294.), which demonstrates that the present process produced the same MOF.
25
3. Continuous flow-spray drying synthesis of MTV-UiO-66
3.1 Preparation of the divariate UiO-66-(BDC-Br)0 5(BDC) .
A solution 0.1 M of ZrCI4, 0.066 M of BDC and 0.033 M of Br-BDC in 15 mL of
30 a mixture of DMF and H2O (12.9:1 ) was injected into the coil flow reactor
(Pyrex tube, inner diameter: 3 mm) at a feed rate of 2.4 mL-min"1 and at a T1 of 1 15 °C. The resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 mL-min"1 using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the 35 collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This process was repeated twice
with ethanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-(BDC-Br)0.5(BDC): Y\e\0 = 0.29 g; SBET = 818 m2 g 1
The crystallinity and the phase purity were confirmed by PXRD (figure 10), showing that the UiO-66-(BDC-Br)0.5(BDC) is isostructural with the bare UiO- 66 reported in the literature (Cavka S. S. Y., et al, supra). The figure 10 shows Scanning Electron Microscopy (SEM) image for the material, revealing the formation of spherical superstructures created by the close packing of nanoparticles.
3.2 Preparation of the divariate UiO-66-(BDC-Br)(BDC). A solution 0.1 M of ZrCI4, 0.05 M of BDC and 0.05 M of Br-BDC in 15 mL of a mixture of DMF and H2O (12.9:1 ) was injected into the coil flow reactor (Pyrex tube, inner diameter: 3 mm) at a feed rate of 2.4 mL-min"1 and at a T1 of 1 15 °C. The resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 mL-min"1 using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This process was repeated twice with ethanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum. Results UiO-66-(BDC-Br)(BDC): Yield = 0.33 g; SBET = 678 m2 g 1
The crystallinity and the phase purity were confirmed by PXRD (figure 1 1 ), showing that the UiO-66-(BDC-Br)(BDC) is isostructural with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra). The figure 1 1 shows Scanning Electron Microscopy (SEM) image for the material, revealing the formation of spherical superstructures created by the close packing of nanoparticles.
3.3 Preparation of the divariate UiO-66-(BDC-Br)2(BDC). A solution 0.1 M of ZrCI4, 0.033 M of BDC and 0.066 M of Br-BDC in 15 ml_ of a mixture of DMF and H2O (12.9:1 ) was injected into the coil flow reactor (Pyrex tube, inner diameter: 3 mm) at a feed rate of 2.4 mL-min"1 and at a T1
of 1 15 °C. The resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 nriL-min" using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This process was repeated twice with ethanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-(BDC-Br)2(BDC): Y\e\0 = 0.31 g; SBET = 570 m2 g 1
The crystallinity and the phase purity were confirmed by PXRD (figure 12), showing that the UiO-66-(BDC-Br)2(BDC) is isostructural with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra). The figure 12 shows Scanning Electron Microscopy (SEM) image for the material, revealing the formation of spherical superstructures created by the close packing of nanoparticles.
3.3 Preparation of the trivariate UiO-66-(BDC-Br)(BDC)(NH2-BDC). A solution 0.1 M of ZrCI4, 0.015 M of BDC, 0.015 M of NH2-BDC and 0.015 M of Br-BDC in 15 mL of a mixture of DMF and H2O (5.48:1 ) was injected into the coil flow reactor (Pyrex tube, inner diameter: 3 mm) at a feed rate of
2.4 mL min and at a T1 of 1 15 °C. The resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 mL min"1 using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This process was repeated twice with ethanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum.
Results UiO-66-(BDC-Br)(BDC)(NH2-BDC): Yield = 0.35 g; SBET = 707 m2 g 1
The crystallinity and the phase purity were confirmed by PXRD (figure 13), showing that the UiO-66-(BDC-Br)(BDC)(NH2-BDC) is isostructural with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra). The figure 13 shows Scanning Electron Microscopy (SEM) image for the material,
revealing the formation of spherical superstructures created by the close packing of nanoparticles.
4. Spray-drying continuous flow-assisted synthesis of Fe-benzene-1 ,3,5- tricarboxylic acid MOF (Fe-1 ,3,5-BTC)
0.62 g of Fe(NO3)3-9H2O (Sigma-Aldrich) in 7.5 mL of dimethylformamide (DMF, Fisher Scientific) was added to a solution of 0.21 g of benzene-1 ,3,5- tricarboxylic acid (1 ,3,5-BTC, Sigma-Aldrich) in 7.5 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 135 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B- 290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3/h, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 6 minutes an orange powder was collected. Then, the orange powder was dispersed in 50 mL of H2O at 100 °C under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 15 mL of ethanol at 70 °C. The final product was dried for 12 h at 70 °C under vacuum.
The yield was 0.25 g (78 % w/w). The specific surface area (BET method) was 1039 m2-g"1.
The X-ray powder diffraction (XRPD) pattern (figure 14) of the MOF confirms that the solid obtained by the present process is comparable to that commercially available Basolite F300.
5. Continuous flow-spray drying synthesis of CPO-27-M series. In a typical synthesis, a solution 0.2 of the metal salt and 0.1 M of 2,5- dihydroxy-1 ,4-benzenedicarboxylic acid in 10 ml of a mixture of DMF and H2O (1 :1 ) was injected into the coil flow reactor (Pyrex tube, inner diameter: 3 mm) at a feed rate of 2.4 mL-min"1 and at a T-, of 90 °C. The resulting pre-heated solution was then spray-dried at a T2 of 180 °C and a flow rate of 336 mL-min" 1 using a Mini Spray Dryer B-290 (BUCHI Labortechnik; spray cap of 0.5 mm of diameter hole). Finally, the collected solid was dispersed in DMF at room temperature under stirring overnight and precipitated by centrifugation. This
process was repeated twice with methanol instead of DMF. The final product was dried for 12 h at 80 °C under vacuum.
5.1. Preparation of a Zn-2,5-dihydroxy-1 ,4-benzenedicarboxylic acid MOF (Zn-MOF-74/CPO-27-Zn)
0.44 g of Zn(CH3COO)2-2H2O (Sigma-Aldrich) in 5.0 mL of water was added to a solution of 0.19 g of 2,5-dihydroxy-1 ,4-benzenedicarboxylic acid (dhtp, Sigma-Aldrich) in 5.0 mL of DMF (Fisher Scientific). The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3mm, length: 100 mm) at a bath temperature of 90 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice. Then, the powder was dispersed in 15 mL of methanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated three times. The final product was dried for 12 h at 80 °C under vacuum.
Results CPO-27-Zn: Yield: 0.26 g (72 % w/w), SBET = 1170 m2-g"1. The X-ray powder diffraction (XRPD) pattern (figure 15) of the MOF (also known as Zn-MOF-74) confirm that the solid obtained by the present process is identical to the Zn-MOF-74 synthesized by the solvothermal method reported in the literature (Rosi N. L., Kim J., Eddaoudi M., Chen B., O'Keeffe M., Yaghi O. M. "Rod packings and metal-organic frameworks constructed from rod-shaped secondary building units", Journal of the American Chemical
Society 2005, 127, 1504-1518.).
5.2. Preparation of a Co-2,5-dihydroxy-1 ,4-benzenedicarboxylic acid MOF (CPO-27-Co)
0.50 g of Co(CH3COO)2-4H2O (Sigma-Aldrich) in 5.0 mL of water was added to a solution of 0.19 g of 2, 5-dihydroxy-1 ,4-benzenedicarboxylic acid (dhtp,
Sigma-Aldrich) in 5.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 90 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h" inlet air temperature of 180 °C, outlet air temperature of 120 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes an orange powder was collected. Then, the orange powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice. Then, the powder was dispersed in 15 mL of methanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated three times. The final product was dried for 12 h at 80 °C under vacuum. Results CPO-27-Co: Yield: 0.25 g (73 % w/w), SBET = 943 m2-g"1.
The figure 16 shows the X-ray powder diffraction (XRPD) pattern of the obtained MOF (also known as CPO-27-Co) compared with the simulated pattern of the CPO-27-Co reported in the literature (Dietzel, P. D. C, Morita, Y., Blom, R., & Fjellvag, H. "An In Situ High-Temperature Single-Crystal
Investigation of a Dehydrated Metal-Organic Framework Compound and Field-Induced Magnetization of One-Dimensional Metal-Oxygen Chains", Angewandte Chemie International Edition, 2005, 44(39), 6354-6358). The patterns are identical, which demonstrates that the present process produced the same MOF.
5.3. Preparation of a Ni-2,5-dihydroxy-1 ,4-benzenedicarboxylic acid MOF (CPO-27-Ni) A solution of 0.50 g of Ni(CH3COO)2-4H2O (Sigma-Aldrich) in 5.0 mL of water was added to a solution of 0.19 g of 2,5-dihydroxy-1 ,4-benzenedicarboxylic acid (dhtp, Sigma-Aldrich) in 5.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 90 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of
120 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes a brown powder was collected. Then, the brown powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice. Then, the powder was dispersed in 15 mL of methanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated three times. The final product was dried for 12 h at 80 °C under vacuum.
Results CPO-27-Ni: Yield: 0.18 g (54 % w/w), SBET = 837 m2-g"1.
The figure 17 shows the X-ray powder diffraction (XRPD) pattern of the obtained MOF, which gave diffraction peaks matching those of the simulated pattern of CPO-27-Ni obtained by solvothermal method reported in the literature (Dietzel, P. D. C, Panella, B., Hirscher, M., Blom, R., & Fjellvag, H. "Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework", Chemical Communications 2006, (9), 959-959), which demonstrates that the present process produced the same MOF. 5.4. Preparation of a Cu-2,5-dihydroxy-1 ,4-benzenedicarboxylic acid MOF (Cu-MOF-74, also called CPO-27-Cu)
A solution of 0.47 g of Cu(NO3)2-2.5H2O (Sigma-Aldrich) in 5.0 mL of water was added to a solution of 0.19 g of 2,5-dihydroxy-1 ,4-benzenedicarboxylic acid (dhtp, Sigma-Aldrich) in 5.0 mL of DMF. The resulting mixture was pumped at a feed rate of 2.4 mL-min"1 through the flow reactor (Pyrex tube, inner diameter: 3mm, length: 100 mm) at a bath temperature of 90 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3-h"1, inlet air temperature of 180 °C, outlet air temperature of
120 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes a dark brown powder was collected. Then, the dark brown powder was dispersed in 15 mL of DMF at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice. Then, the powder was dispersed in 15 mL of methanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was
repeated three times. The final product was dried for 12 h at 80 °C under vacuum.
Results CPO-27-Cu: Yield: 0.12 g (38 % w/w), SBET = 973 m2-g"1.
The crystallinity and the phase purity were confirmed by PXRD (figure 18), showing that the obtained MOF is isostructural with the Zn-MOF-74 reported in the literature (Rosi N., et al, supra), which demonstrates that the present process produced the same MOF.
6. Preparation of a Zr-2-Amino-1 ,4-benzenedicarboxylic acid MOF (Zr- 1 ,4-BDC-NH2, also known as UiO-66-NH2) with water as solvent.
A solution of 1 .70 g of ZrOCI2-8H2O (Sigma-Aldrich) in 6.0 mL of water was added to a dispersion of 0.87 g of 2-Amino-1 ,4-benzenedicarboxylic acid (Sigma-Aldrich) in 6.0 mL of Water. Then, 12 mL of Glacial Acetic acid (Sigma-Aldrich) was added to the mixture. The resulting dispersion was pumped at a feed rate of 2.4 mL min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 100 mm) at a bath temperature of 90 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B-290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3/h, inlet air temperature of 150 °C, outlet air temperature of 100 °C, and with a spray cap with 0.5 mm-hole-size. After 10 minutes a yellow powder was collected. Then, the yellow powder was dispersed in 15 mL of Ethanol and then precipitated by centrifugation. This process was repeated three times. Then, the powder was dispersed in 15 mL of Ethanol at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated once with 15 mL of acetone. The final product was dried for 12 h at 80 °C.
Results UiO-66-NH2: Y\e\0 = 83 %; SBET = 1148 m2 g 1.
The crystallinity and the phase purity were confirmed by PXRD (figure 20), showing that the Zr-1 ,4-BDC-NH2 (UiO-66-NH2) is isostructural with the bare UiO-66 reported in the literature (Cavka S. S. Y., et al, supra). The figure 20 shows Scanning Electron Microscopy (SEM) image for the material, revealing
the formation of spherical superstructures created by the close packing of nanoparticles.
7. Preparation of a Zr-Fumaric acid MOF (Zirconium fumarate MOF, also known as MOF-801)
A solution of 0.64 g of ZrOCI2-8H2O (Sigma-Aldrich) in 3.5 mL of water was added to a dispersion of 0.24 g fumaric acid in 3.5 mL of water. Then, 3 mL of glacial acetic acid (Sigma-Aldrich) was added to the mixture. The resulting dispersion was pumped at a feed rate of 2.4 mL min"1 through the flow reactor (Pyrex tube, inner diameter: 3 mm, length: 120 mm) at a bath temperature of 90 °C. The pre-heated solution was spray dried on the Mini Spray Dryer B- 290 (BUCHI labortechnik AG, Flawil, Switzerland) using a two-fluid nozzle at a gas spray flow of 26.25 m3/h, inlet air temperature of 140 °C, outlet air temperature of 100 °C, and with a spray cap with 0.5 mm-hole-size. After 4 minutes a white powder was collected. Then, the white powder was dispersed in 40 mL of water at room temperature under stirring for 12 h and then precipitated by centrifugation. This process was repeated twice with 40 mL of ethanol. The final product was dried for 12 h at 80 °C.
Results MOF-801 : Yield = 54 %; SBET = 540 m2-g"1
The figure 21 shows the scanning Electron Microscopy (SEM) image of the spherical superstructure of zirconium fumarate and their X-ray powder diffraction (XRPD) pattern, which gave diffraction peaks matching those of the simulated pattern of MOF-801 obtained by solvothermal method reported in the literature (H. Furukawa, F.Gandara, Y-B. Zhang, J. Jiang, W. Queen, M. Hudson, and O. Yaghi "Water Adsorption in Porous Metal-Organic Frameworks and Related Materials", Journal of the American Chemical Society, 2014, 136(1 1 ), 4369-4381 ), which demonstrates that the present process produced the same MOF.
REFERENCES CITED IN THE APPLICATION WO2010058123
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EP1373277 EP2764004 Cavka, J. H., Jakobsen, S., Olsbye, U., Guillou, N., Lamberti, C, Bordiga, S., & Lillerud, K. P. "A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability", Journal of the American Chemical Society, 2008, 130(42), 13850-13851 . Guillerm, V., Ragon, F., Dan-Hardi, M., Devic, T., Vishnuvarthan, M., Campo, B., Vimont, A., Clet, G., Yang, Q., Maurin, G., Ferey, G., Vittadini, A., Gross, S. and Serre, C. "A series of isoreticular, highly stable, porous zirconium oxide based metal-organic frameworks", Angewandte Chemie, International Edition, 2012, 51 (37), 9267-9271 .
Padial, N. M., E. Quartapelle Procopio, C. Montoro, E. Lopez, J. E. Oltra, V. Colombo, A. Maspero, N. Masciocchi, S. Galli, I. Senkovska, S. Kaskel, E. Barea and J. A. R. Navarro. "Highly Hydrophobic Isoreticular Porous Metal- Organic Frameworks for the Capture of Harmful Volatile Organic
Compounds." Angewandte Chemie International Edition (2013) 52(32): 8290-
8294
Rosi N. L, Kim J., Eddaoudi M., Chen B., O'Keeffe M., Yaghi O. M. "Rod packings and metal-organic frameworks constructed from rod-shaped secondary building units", Journal of the American Chemical Society 2005,
127, 1504-1518.
Dietzel, P. D. C, Morita, Y., Blom, R., & Fjellvag, H. "An In Situ High- Temperature Single-Crystal Investigation of a Dehydrated Metal-Organic Framework Compound and Field-Induced Magnetization of One-Dimensional Metal-Oxygen Chains", Angewandte Chemie International Edition, 2005, 44(39), 6354-6358.
H. Furukawa, F.Gandara, Y-B. Zhang, J. Jiang, W. Queen, M. Hudson, and O. Yaghi "Water Adsorption in Porous Metal-Organic Frameworks and Related Materials", Journal of the American Chemical Society, 2014, 136(1 1 ), 4369-4381
Claims
1 . A process for the preparation of dry crystalline metal organic frameworks which comprises:
a) contacting at least one metal ion and at least one organic ligand which is at least bidentate in the presence of a solvent at a temperature comprised from 70 °C to 150 °C during a time comprised from 20 to 1 10 s,
b) spray drying the mixture obtained from step a) under conditions
appropriate to form dry crystalline metal organic frameworks, and
c) collecting the formed dry crystalline metal organic frameworks.
2. The process according to claim 1 , wherein the dry crystalline metal organic frameworks are in the form of spherical beads of size comprised from 0.1 to 400 pm.
3. The process according to any of the claims 1 -2, wherein the contacting step is performed during a time comprised from 30 to 90 s.
4. The process according to any of the claims 1 -3, wherein the contacting step is performed at a temperature comprised from 80 to 120 °C.
5. The process according to any of the claims 1 -4, wherein the at least one metal ion is selected from the group consisting of Zr, Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Zr, Gd, Eu, Tb, and mixtures thereof.
6. The process according to any of the claims 1 -5, wherein the at least one organic ligand which is at least bidentate contains at least one functional group selected from the group consisting of a carboxylate, a phosphonate, an amine, an azide, a cyanide, a squaryl, an heteroatom, and mixtures thereof.
7. The process according to claim 6, wherein the at least one organic ligand which is at least bidentate is a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, imidazole, or mixtures thereof.
8. The process according to any of the claims 1 -7, wherein the solvent is selected from water, ethanol, DMF and mixtures thereof.
9. The process according to any of the claims 1 -8, that takes place in the presence of a base or an acid.
10. The process according to any of the claims 1 -9, wherein step b) is performed at a temperature between 80 and 200 °C.
1 1 . The process according to any of the claims 1 -10, further comprising a purification step which comprises washing the crystalline metal organic framework with an appropriate solvent, followed by drying the obtained crystalline metal organic framework.
12. The process according to any of the claims 1 -1 1 , which is a continuous process.
13. Crystalline metal organic frameworks obtained by the process as defined in any of the claims 1 -12.
14. The dry crystalline metal organic frameworks according to claim 13 that are in the form of spherical beads of size comprised from 0.1 to 100 μιτι
15. The crystalline metal organic frameworks according to any of the claims 13-14 that are UiO-66, MTV-UiO-66, [Ni8(OH)4(H2O)2(L)6]n, CPO-27-M and MIL-100.
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| US20090130411A1 (en) * | 2006-03-10 | 2009-05-21 | Korea Research Institute Of Chemical Technology | Adsorbent for Water Adsorption and Desorption |
| EP2578593A1 (en) * | 2011-10-04 | 2013-04-10 | Fundació Privada Institut Català de Nanotecnologia | Method for the preparation of metal organic frameworks |
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2017
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| US20090130411A1 (en) * | 2006-03-10 | 2009-05-21 | Korea Research Institute Of Chemical Technology | Adsorbent for Water Adsorption and Desorption |
| EP2578593A1 (en) * | 2011-10-04 | 2013-04-10 | Fundació Privada Institut Català de Nanotecnologia | Method for the preparation of metal organic frameworks |
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| Publication number | Publication date |
|---|---|
| KR20180134866A (en) | 2018-12-19 |
| JP2019512494A (en) | 2019-05-16 |
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