WO2019162344A1 - Process for preparing a mof with gamma-valerolactone - Google Patents
Process for preparing a mof with gamma-valerolactone Download PDFInfo
- Publication number
- WO2019162344A1 WO2019162344A1 PCT/EP2019/054244 EP2019054244W WO2019162344A1 WO 2019162344 A1 WO2019162344 A1 WO 2019162344A1 EP 2019054244 W EP2019054244 W EP 2019054244W WO 2019162344 A1 WO2019162344 A1 WO 2019162344A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mof
- organic
- zirconium
- reaction mixture
- acid
- Prior art date
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 77
- -1 linker compound Chemical class 0.000 claims abstract description 33
- 239000011541 reaction mixture Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 64
- 230000008569 process Effects 0.000 claims description 50
- 229910021645 metal ion Inorganic materials 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 125000000524 functional group Chemical group 0.000 claims description 17
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 150000007942 carboxylates Chemical group 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 239000001530 fumaric acid Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- LPJFECYYLUQKSO-UHFFFAOYSA-N 4-(4-carboxynaphthalen-1-yl)naphthalene-1-carboxylic acid Chemical compound C12=CC=CC=C2C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C2=CC=CC=C12 LPJFECYYLUQKSO-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 150000002763 monocarboxylic acids Chemical group 0.000 claims 1
- 125000005647 linker group Chemical group 0.000 description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 238000000634 powder X-ray diffraction Methods 0.000 description 18
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 17
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 235000011054 acetic acid Nutrition 0.000 description 9
- 238000004626 scanning electron microscopy Methods 0.000 description 9
- 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 8
- 238000001914 filtration Methods 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 238000002429 nitrogen sorption measurement Methods 0.000 description 8
- 239000013207 UiO-66 Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000001905 inorganic group Chemical group 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000013341 scale-up Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- DAWHTISAONTGQE-UHFFFAOYSA-N 3-(2-phenylphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1C(O)=O DAWHTISAONTGQE-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 229910052688 Gadolinium 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 239000013208 UiO-67 Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 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 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZOQCTFVIEBUWIT-UHFFFAOYSA-N 1,2,3,3a-tetrahydropyrene-2,7-dicarboxylic acid Chemical compound C1=C2CC(C(=O)O)CC(C=C3)C2=C2C3=CC(C(O)=O)=CC2=C1 ZOQCTFVIEBUWIT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PAAYYTAKLZCRDE-UHFFFAOYSA-N 2-butylterephthalic acid Chemical compound CCCCC1=CC(C(O)=O)=CC=C1C(O)=O PAAYYTAKLZCRDE-UHFFFAOYSA-N 0.000 description 1
- JRMAQQQTXDJDNC-UHFFFAOYSA-N 2-ethoxy-2-oxoacetic acid Chemical compound CCOC(=O)C(O)=O JRMAQQQTXDJDNC-UHFFFAOYSA-N 0.000 description 1
- 239000013273 3D metal–organic framework Substances 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- ADZQMDVFAIDYBT-UHFFFAOYSA-N 4-naphthalen-1-yl-2H-naphthalene-1,1-dicarboxylic acid Chemical compound C1(=CCC(C2=CC=CC=C12)(C(=O)O)C(=O)O)C1=CC=CC2=CC=CC=C12 ADZQMDVFAIDYBT-UHFFFAOYSA-N 0.000 description 1
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052695 Americium Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910052685 Curium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium 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
- 229910052689 Holmium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- 229930182821 L-proline Natural products 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 229910052764 Mendelevium 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
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052774 Proactinium 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- XMAAINZKCZUYAX-UHFFFAOYSA-M [O-]C(C(C=C1)=CC=C1[Zn+])=O.C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1 Chemical compound [O-]C(C(C=C1)=CC=C1[Zn+])=O.C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1 XMAAINZKCZUYAX-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001252 acrylic acid derivatives 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
- AXLLOYXRJRMBEW-UHFFFAOYSA-N adamantane;benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1.C1C(C2)CC3CC1CC2C3 AXLLOYXRJRMBEW-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 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
- 125000003277 amino group Chemical group 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- VNXSDDLAAPKDBL-UHFFFAOYSA-N benzene;2-phenylbenzoic acid Chemical compound C1=CC=CC=C1.OC(=O)C1=CC=CC=C1C1=CC=CC=C1.OC(=O)C1=CC=CC=C1C1=CC=CC=C1.OC(=O)C1=CC=CC=C1C1=CC=CC=C1 VNXSDDLAAPKDBL-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 125000005620 boronic acid group Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical compound C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 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
- 239000011572 manganese Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 229910052750 molybdenum Inorganic materials 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
- 239000003345 natural gas Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [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
- 125000001147 pentyl group Chemical class C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229960002429 proline Drugs 0.000 description 1
- 125000001436 propyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009877 rendering Methods 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
- 238000000926 separation method Methods 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
- JARIJYUQOKFVAJ-UHFFFAOYSA-M sodium;4-carboxy-2-sulfobenzoate Chemical compound [Na+].OC(=O)C1=CC=C(C([O-])=O)C(S(O)(=O)=O)=C1 JARIJYUQOKFVAJ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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 relates to a process for preparing metal organic frameworks (MOFs), in particular to a process for preparing Zr-MOFs. Specifically, the process employs gamma- Valero lactone (GVL) as a solvent.
- the invention also relates to MOFs produced by such processes.
- MOFs or "metal organic frameworks” are compounds having a lattice structure having vertices or “cornerstones” which are metal-based inorganic groups, for example metal oxides, linked together by organic linkers.
- the linkers are usually at least bidentate ligands which coordinate to the metal-based inorganic groups via functional groups such as carboxylate and/or amine.
- the porous nature of MOFs renders them promising materials for many applications such as gas storage and catalyst materials.
- MOF-5 in which each Z114O cornerstone is coordinated by six bis-carboxylate organic linkers.
- Other MOFs in which the inorganic cornerstone is for example chromium, copper, vanadium, cadmium or iron are also known.
- DMF dimethylformamide
- Apparatus suitable for withstanding the severe reaction conditions is often only compatible with small scale batch synthesis, rather than the continuous processes favoured for large scale production.
- Employing high pressures also carries with it safety concerns, particularly when combined with the use of corrosive liquids.
- the use of organic solvents as the reaction medium is undesirable as such solvents are harmful to the environment and are expensive.
- DMF Dimethylformamide
- DMSO Dimethyl sulfoxide
- DMA Dimethylamide
- MOFs become increasingly employed as alternatives to, for example, zeolites, polymers and activated carbons there is a need for the development of novel processes for their production which are applicable to use on an industrial scale.
- the process should ideally be one which is“green” and thus considered environmentally friendly. It should preferably provide high volume MOF production per volume of solvent used. It would also be advantageous to have a process with easier waste management by biodegradation, incineration etc. Ideally, a process which offers improvement in more than one of the above aspects would be developed.
- MOFs may be prepared in a straightforward process utilising gamma- valero lactone (GVF) as a solvent.
- VVF gamma- valero lactone
- Gamma- Valero lactone (GVF - structure shown in figure 1) is a colourless organic liquid and has been identified as a potential green solvent. It is readily obtained from cellulosic biomass. It can be produced at a price between 1-2 US$/L. GVL boils at 207 °C and has a flash point of 96 °C which are both higher than for DMF (B.P. 150 °C and flash point 67 °C ) thereby rendering it easier to operate at high temperature. GVL is chemically and thermally more stable than the organic solvents (such as DMF, DMA and DMSO) usually employed in MOF synthesis. The higher stability of GVL may allow for solvent recycling in MOF production processes.
- the organic solvents such as DMF, DMA and DMSO
- GVL is also considered as a potential fuel, therefore the solvent waste may be used as a fuel to produce energy thus making the overall processes more economical.
- GVL upon burning will produce C0 2 while DMF and DMSO will produce toxic nitrogen and sulfur-containing compounds.
- biodegradation could be pursued to manage the waste.
- the invention provides a process for preparing a metal organic framework (MOF), comprising the steps:
- the metal organic framework is a zirconium-based metal organic framework (Zr-MOF).
- the invention provides a metal organic framework (MOF) produced or formable by the processes as herein described.
- MOF metal organic framework
- the present invention describes a process for the preparation of a metal organic framework (MOF), such as a zirconium-based metal organic framework (Zr-MOF).
- MOF metal organic framework
- Zr-MOF zirconium-based metal organic framework
- the process involves preparing a reaction mixture comprising a metal salt and at least one organic linker compound in gamma- valerolactone (GVL) solvent and heating the reaction mixture.
- VTL gamma- valerolactone
- MOF is intended to cover any metal organic framework.
- MOFs typically comprise at least one metal ion or cluster of metal ions and at least one organic linker compound.
- the metal ion or cluster of metal ions may be any suitable metal selected from Groups 1 to 16 of the Periodic Table.
- the metal ion may have any valence appropriate for the specific metal.
- 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, lr, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg) and post-transition metals (Al, Ga, In, Tl, Sn, Pb, Bi), as well as metalloids (B, Si, Ge, As, Sb, Te, Po), lanthanides (La, Ce, Pr, Nd, Pm, Sm, Eu
- the metal ion is selected from the group consisting of Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Al, Zr, Gd, Eu, Tb, Ce, Y, Hf, and mixtures thereof.
- the metal ion is selected from the group consisting of, zirconium, magnesium, zinc, aluminium, iron, cerium, hafnium and yttrium. Most preferably, the metal ion is zirconium.
- the MOF contains only a single type of metal ion.
- the process of the invention is used to prepare zirconium-based metal organic frameworks (Zr-MOFs).
- Zr-MOF zirconium-based metal organic frameworks
- the term“Zr-MOF” is intended to cover any metal organic frameworks (MOFs) which comprise at least one zirconium metal ion.
- the Zr-MOFs of the invention have“cornerstones” which are zirconium inorganic groups. Typical zirconium inorganic groups include zirconium ions connected by bridging oxygen or hydroxide groups. These inorganic groups are further coordinated to at least one organic linker compound. In some cases, the inorganic groups may be further connected to non bridging modulator species, complexing reagents or ligands (e.g.
- the zirconium oxide unit is usually based on an idealized octahedron of Zr-ions which are p3-bridged by O 2 and/or OH ions via the faces of the octahedron and further saturated by coordinating moieties containing O-atoms like carboxylate groups.
- the idealised Zr oxide cluster is considered to be a Zr 6 0 32 -cluster which comprises between 6 and 12 (preferentially as close as possible to 12) carboxylate groups.
- the cluster may be represented by the formula Zr 6 O x (OH) 8-x wherein x is in the range 0 to 8.
- the cluster may be represented by the formula
- zirconium Whilst it not outside the bounds of the present invention for the Zr-MOF to comprise additional metal ions other than zirconium, such as hafnium, titanium, or cerium, zirconium may be the only metal ion present. If additional metal ions are present these may be present in an amount of up 50 wt% relative to total amount of metal ions, preferably up to 25 wt%, more preferably up to 10 wt%, e.g. up to 5 wt%.
- the Zr-MOFs of the invention particularly preferably have cornerstones having at least 12 coordination sites for the organic linkers, e.g. 12-36, especially preferably at least 14, 16 or 18, most especially 24. In this way at least 6, more preferably at least 8, especially at least 12 bidentate ligand groups of the organic linkers can bind to each cornerstone.
- the Zr-MOF of the invention particularly preferably has cornerstones having at least 6 coordination sites for the organic linkers, e.g. 6-36, especially preferably at least 6, 12, 18, most especially 24. In this way at least 6, more preferably at least 8, especially at least 12 bidentate or at least 6 tridentate or hexadentate ligand group of the organic linkers can bind to each cornerstone.
- the structure of the MOFs of the invention may be one- two- or three- dimensional.
- the MOF usually comprises pores which are present in the voids between the coordinated network of zirconium ions and organic linker compounds. The pores are typically micropores, having a diameter of 2 nm or less, or mesopores, having a diameter of 2 to 50 nm.
- the surface area of the MOF is preferably at least 400 m 2 /g, more preferably at least 500 m 2 /g, especially at least 700 m 2 /g, such as at least 1020 m 2 /g, for example at least 1050 m 2 /g, e.g. at least 1200 m 2 /g, as measured by nitrogen adsorption at 77 K, using BET method.
- the surface area may be up to 10000 m 2 /g, especially up to 5000 m 2 /g. It will be understood that, where functionalised organic linker compounds are used, the presence of additional, and often bulky, groups may affect (i.e. reduce) the surface area of the MOF.
- the MOFs of the invention comprise at least one organic linker compound.
- the organic linker compound is typically at least bidentate, i.e. has at least two functional groups capable of coordinating to the metal ion.
- the organic linker compound may also be tridentate (i.e. containing three functional groups) or tetradentate (i.e. containing four functional groups).
- the organic linker coordinates between 2 and 20 metal ions.
- the organic ligand coordinates between 2 and 12 metal ions.
- the MOF may have a metal ion to organic linker molecule ratio of from 1 :0.30 to 1 :0.55, especially 1 :0.33 to 1 :0.51, particularly 1 :0.33.
- Other preferred metal ion to organic linker molecule ratios are 0.5: 1, 1 : 1, 3: 1 and 1 :3, especially 1 : 1.
- the organic linker compounds of the MOFs of the invention may be any organic linker molecule or molecule combination capable of binding to at least two inorganic cornerstones and comprising an organic moiety.
- organic moiety we mean a carbon based group which comprises at least one C-H bond and which may optionally comprise one or more heteroatoms such as N, O, S, B, P, Si. Typically, the organic moiety will contain 1 to 50 carbon atoms.
- the organic linker compound may be any of the linkers conventionally used in MOF production. These are generally compounds with at least two cornerstone binding groups, e.g. carboxylates, optionally with extra functional groups which do not bind the cornerstones but may bind metal ions on other materials it is desired to load into the MOF. The introduction of such extra functionalities is known in the art and is described for example by Campbell in JACS 82:3126-3128 (1960).
- the organic linker compound may be in the form of the compound itself or a salt thereof, e.g. a disodium 1 ,4-benzenedicarboxylate salt or a monosodium 2- sulfoterephthalate salt.
- the organic linker compound is preferably soluble in the GVL solvent employed in the processes of the invention.
- soluble we mean that it preferably has a solubility which is high enough to enable the formation of a homogenous solution.
- the solubility of the organic linker compound in GVL may be at least 1 g/L at room temperature and pressure (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
- the organic linker compound typically comprises at least two functional groups capable of binding to the inorganic cornerstone.
- binding we mean linking to the inorganic cornerstone by donation of electrons (e.g. an electron pair) from the linker to the cornerstone.
- the linker comprises two, three or four functional groups capable of such binding.
- Non-limiting functional groups that can be contained by the organic ligand to form a MOF according to the invention are -COOH, -CSSH, -N0 2 , - B(OH) 2 , - S0 3 H, -Ge(OH) 3 , -Sn(OH) 3 , -Si(SH) 4 , -Ge(SH) 4 , -Sn (SH) 3 , -P0 3 H, - As0 3 H, - AS0 4 H, -P(SH) 3 , AS(SH) 3 , C 4 H 2 0 4 , -RSH, -RNH 2 , -RNR-, -ROH, - RCN, - PO(OR) 2 , -RN 3 , where R is hydrogen, alkyl, alkylene, preferably Cl, C2, C3, C4 or C5 alkylene, or aryl group, preferably comprising 1 or 2 aromatic nuclei.
- the organic linker comprises at least two functional groups selected from the group of carboxylate (COOH), amine (NH 2 ), nitro (N0 2 ), anhydride and hydroxyl (OH) or a mixture thereof.
- the linker comprises two, three or four carboxylate groups.
- the organic linker compound may be based on a saturated or unsaturated aliphatic compound or an aromatic compound. Alternatively, the organic linker compound may contain both aromatic and aliphatic moieties.
- the aliphatic organic linker compound may comprise a linear or branched Ci_ 2 o alkyl group or a C 3 _i 2 cycloalkyl group.
- the term "alkyl” is intended to cover linear or branched alkyl groups such as all isomers of propyl, butyl, pentyl and hexyl. In all embodiments, the alkyl group is preferably linear. Particularly preferred cycloalkyl groups include cyclopentyl and cyclohexyl.
- the organic linker compound comprises an aromatic moiety.
- the aromatic moiety can have one or more aromatic rings, for example two, three, four or five rings, with the rings being able to be present separately from one another and/or at least two rings being able to be present in condensed form.
- the aromatic moiety particularly preferably has one, two or three rings, with one or two rings being particularly preferred, most preferably one ring.
- Each ring of said moiety can independently comprise at least one heteroatom such as N, O, S, B, P, Si, preferably N, O and/or S.
- the aromatic moiety preferably comprises one or two aromatic C6 rings, with the two rings being present either separately or in condensed form.
- Particularly preferred aromatic moieties are benzene, naphthalene, biphenyl, bipyridyl and pyridyl, especially benzene.
- suitable organic linker compounds include oxalic acid, ethyloxalic acid, fumaric acid, 1,3, 5-benzene tricarboxylic acid (BTC), 1,1’- binaphthyl 4,4'-dicarboxylic acid (BINAP-H 2 ), 1,3, 5-benzene tribenzoic acid (BTB), benzene tribiphenylcarboxylic acid (BBC), 5, 15-bis (4-carboxyphenyl) zinc (II) porphyrin (BCPP), 1, 4-benzene dicarboxylic acid (BDC), 2-amino- 1, 4-benzene dicarboxylic acid (R3-BDC or H2N BDC), 1,2, 4, 5-benzene tetracarboxylic acid, 2- nitro-l, 4-benzene dicarboxylic acid l,l'-azo-diphenyl 4,4'-dicarboxylic acid, eye lo butyl- 1, 4-benzene dicarboxylic acid (R
- the organic linker compound is selected from the group consisting of 1 ,4-benzene dicarboxylic acid (BDC), fumaric acid, 1,3, 5-benzene tricarboxylic acid (BTC), 1 , G-binaphthyl 4,4'-dicarboxylic acid (BINAP-H 2 ) or mixtures thereof.
- a mixture of two or more of the above-mentioned linkers may be used. It is preferable, however, if only one type of linker is used.
- MOF is a Zr-MOF with a bidentate organic linker it is preferably of UiO-66 type.
- UiO-66 type Zr-MOFs cover structures in which the zirconium inorganic groups are Zr 6 (0) 4 (0H) 4 and the organic linker compound is 1 ,4-benzene dicarboxylic acid or a derivative thereof.
- Derivatives of 1 ,4-benzene dicarboxylic acid used in UiO-66 type Zr-MOFs include 2-amino- 1, 4-benzene dicarboxylic acid, 2 -nitro-l, 4-benzene dicarboxylic acid, 1,2, 4-benzene tricarboxylic acid and 1,2, 4,5- benzene tetracarboxylic acid.
- the resulting MOF may be referred to as UiO-66(Zr).
- the linker is 2-amino- 1, 4-benzene dicarboxylic acid
- the resulting MOF may be referred to as UiO-66(Zr)-NH 2 .
- the linker is 1,2, 4-benzene tricarboxylic acid
- the resulting MOF may be referred to as UiO- 66(Zr)-COOH.
- the linker is 1,2, 4, 5-benzene tetracarboxylic acid
- the resulting MOF may be referred to as UiO-66(Zr)-2COOH.
- MOF is a Zr-MOF with a tridentate organic linker it is preferably of MOF-8O8 type.
- MOF is a Zr-MOF with, tetradentate or hexadentate organic linker it is preferably of NU- 1000, pbz-MOF-l type structure respectively.
- a mixture of linkers may be used to introduce one or more functional groups within the pore space, e.g. by using aminobenzoic acid to provide free amine groups or by using a shorter linker such as oxalic acid.
- This introduction of functionalised linkers is facilitated by having a MOF with inorganic cornerstones with a high number of coordination sites. Where the number of these coordination sites exceed the number required to form the stable 3D MOF structure, functionalisation of the organic linkers may be effected, e.g. to carry catalytic sites, without seriously weakening the MOF structure.
- By“functionalised MOF” we mean a MOF wherein one or more of the backbone atoms of the organic linkers carries a pendant functional group or itself forms a functional group.
- Functional groups are typically groups capable of reacting with compounds entering the MOF or acting as catalytic sites for reaction of compounds entering the MOF. Suitable functional groups will be apparent to a person skilled in the art and in preferred embodiments of the invention include amino, nitro, thiol, oxyacid, halo (e.g. chloro, bromo, fluoro) and cyano groups or heterocyclic groups (e.g. pyridine), each optionally linked by a linker group, such as carbonyl.
- the functional group may also be a phosphorus-or sulfur-containing acid.
- a particularly preferred functional group is halo, most preferably a fluoro group.
- the functionalised MOF has a surface area of at least 400 m 2 /g, more preferably at least 500 m 2 /g, especially at least 700 m 2 /g, such as at least 1020 m 2 /g.
- the process of the invention comprises at least the steps of:
- the organic linker compound may be any organic linker as hereinbefore defined. It will be understood that the organic linker described in the context of the MOF produced by the processes of the invention is the same organic linker which is used as a starting material in step (i) of the process of the invention, albeit that once bound to the inorganic cornerstone the organic linker will be deprotonated. Thus all preferable embodiments defined above relating to the organic linker in the context of the MOF apply equally to this compound as a starting material.
- the metal ions of the MOF are provided in the form of at least one metal salt, which may or may not be in its hydrated form. Whilst the use of a mixture of two or more different salts is encompassed by the invention, it is preferable if one salt is used.
- the metal salt is usually soluble in GVL, i.e. preferably having a solubility of at least 1 g/L at room temperature (i.e. 18 to 30 °C) and pressure (i.e. 0.5 to 3 bar) (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
- Suitable counter-ions will be familiar to the skilled worker and may include halides (e.g. chlorides and bromides), acetates, nitrates, formats, oxalates, acetylacetonates, carbonates, tatrates, oxides, acrylates, carboxylates, sulfates, hydroxides, perchlorates, oxynitrates and oxychlorides.
- halides e.g. chlorides and bromides
- metal salt is a zirconium salt
- examples of preferable metal salts include zirconium sulfate, zirconium hydroxide, zirconium acetylacetonate, zirconium chloride (ZrCl 4 ) and zirconyl chloride (ZrOCf nFLO, wherein n is an integer from 1 to 10, preferably 8).
- the reaction mixture preferably further comprises a growth modulator.
- growth modulator we mean a compound that affects the rate of crystal growth, making it slower or faster. Suitable growth modulators are known in the art.
- growth modulator compounds for use in the invention are monocarboxylic acids compounds (such as acetic acid, benzoic acid, formic acid, trifluroacetic acid or amino acids), inorganic acids (such as hydrochloric acids, hydrofluoric acid, sulfuric acids).
- Basic compounds such as alkali hydroxide (e.g. NaOH or KOH) or ammonium hydroxide could also be used as a growth modulator
- the reaction mixture prepared in step (i) of the processes of the invention is typically prepared by mixing the various components together in the GVL solvent. Mixing may be carried out by any known method in the art, e.g. mechanical stirring. The mixing is preferably carried out at temperature between 18 and 50 °C. Usually, step (i) is carried out at or around atmospheric pressure, i.e. 0.5 to 2 bar, especially 1 bar.
- step (ii) of the process the reaction mixture prepared in step (i) is heated. Heating is usually carried out to a temperature at which the reaction mixture boils. Preferably, the temperature is increased to 50 - 150 °C, more preferably 60 - 130 °C, such as 80-120 °C. Usually, step (ii) is carried out at or around atmospheric pressure, i.e. 0.5 to 2 bar, especially 1 bar.
- the reaction mixture is preferably heated for a period of time of at least 20 minutes, more preferably at least 30 minutes, even more preferably at least 50 minutes, i.e. at least 60 minutes.
- the reaction mixture is preferably heated for not more than 10 hours, more preferably not more than 5 hours, especially not more than 2 hours.
- Step (ii) is generally carried out by heating the reaction mixture from step (i) under reflux at the temperature and for the time periods as hereinbefore defined.
- the method of heating may be by any known method in the art, such as heating in a conventional oven, a microwave oven or heating in an oil bath.
- GVL The high boiling point (207 °C) and high flash point (97 °C) of GVL offers numerous advantages over those of previous methods wherein DMF, DMSO and DMA solvents were used as the reaction medium.
- the mild reactions conditions and high stability of the solvent used in the process of the invention offer the possibility of solvent recycling.
- GVL is also considered as a potential fuel; therefore the solvent waste can be used as a fuel to produce energy thus making the overall processes more economical.
- GVL upon burning will produce C0 2 while DMF and DMSO will produce toxic nitrogen and sulfur-containing compounds.
- biodegradation can be pursued to manage the waste. This offers improvements in terms of costs, safety and suitability for industrial scale-up.
- the molar ratio of total metal ions to total organic linker compound(s) present in the reaction mixture prepared in step (i) is typically between 1 :0.30 and 1 :1, however in some embodiments an excess of the organic linker compound may be used.
- the molar ratio of total metal ions to total organic linker compound(s) in the reaction mixture is in the range 1 : 0.30 to 1 :5, such as 1 :1 or 1 :4. It will be appreciated that the MOF product forms during step (ii) of the process.
- the processes of the invention usually comprise a further step (iii) isolating the MOF.
- the MOF is usually formed as a crystalline product which can be isolated quickly and simply by methods such as filtration, or centrifugation.
- This offers an improvement over some methods of the prior art which produce an amorphous or gel-like product which must be further recrystallized before it can be isolated.
- the processes of the present invention thus preferably eliminate the need for these additional steps.
- the isolation step (iii) is typically carried out by filtration, but isolation may also be performed by processes such as centrifugation, solid-liquid separations or extraction. After isolation, the MOF is preferably obtained as a fine crystalline powder having crystal size of 0.1 to 100 pm, such as 10 to 50 pm.
- the processes of the invention may comprise additional steps, such as drying and/or cooling.
- additional steps such as drying and/or cooling.
- cooling step usually involves bringing the temperature of the reaction mixture back to room temperature, i.e. 18-30 °C.
- the invention relates to a metal organic framework (MOF) produced or formable by the processes as herein described.
- MOF metal organic framework
- MOF produced or formable by the processes of the present invention may be employed in any known application for such materials. Applications therefore include, but are not restricted to, electrode materials, drug reservoirs, catalyst materials, adsorbents and cooling media.
- FIG. 1 Drawing of molecular structure of gamma- valero lactone (GYL).
- Figure 3a-b Powder X-ray diffraction patterns of the UiO-66-BDC product from the synthesis 1-11.
- FIG. 11 Structure of MOF-808.
- Figure 12. Powder X-ray diffraction pattern and Thermogravimetric analysis of MOF-808 obtained by process of invention.
- the specific surface area was determined by means of N 2 physisorption measured on a Belsorp-mini apparatus at 77 K. Prior to the measurement the sample was activated at 423 K under vacuum for 3 h to remove occluded water molecules. The surface area was calculated by the BET-method (DIN 66131) and the Langmuir method (DIN 66135).
- SEM Scanning electron microscopy
- UiO-66-BDC ( Figure 2) is a prototype MOF of UiO-66 series with hexanuclear Zr 6 cluster as a inorganic comer stone connected by Benzene- 1 ,4-dicarboxylic acid (BDC-H 2 ) as an organic linker. This is one of the most thermally and chemically stable MOF. It contains octahedral and tetrahedral cadges accessible via triangular window.
- a synthesis screening was performed with the metal: linker: solvent molar ratio set to 1 : 1 :52 respectively while changing the modulator type (acetic acid, formic acid) and modulator amount (0, 10, 20, 30).
- the reaction mixture was transfer in glass vial and heated at 120 °C inside heating oven. The details of the reagent amount are given in a Table 1.
- the final product was separated by centrifugation and washed with GVL once at room temperature before drying at 100 °C. The process provides a space time yield of 250-334 kg/ m 3 day.
- Figure 3a and b show the PXRD patterns of the obtained products.
- Synthesis 10 1.161 gm of Zr0Cl 2 .8H20; 0.599 gm of 1 ,4-benzenedicarboxylic acid and 4.078 ml of formic acid were mixed in 17.95 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 150 °C.
- Figure 4 shows the PXRD, TGA, SEM and nitrogen sorption isotherm of the product calcined at 270 °C.
- Synthesis 11 1.756 gm of Zr(acac) 4 ; 0.599 gm of 1 ,4-benzenedicarboxylic acid and 1.359 ml of formic acid were mixed in 17.95 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 150 °C.
- Figure 5 shows the PXRD, TGA, SEM and nitrogen sorption isotherm of the product calcined at 270 °C. Table 1. Reagents quantities used to screen for the synthesis of UiO-66-BDC.
- Zr-Fumarate ( Figure 6) also contains hexanuclear Zr 6 cluster as an inorganic comer stone but they are connected by Fumarate(FA). Fumaric acid is shorter linker than Benzene- 1 ,4-dicarboxylic acid therefore Zr-Fumarate contains octahedral and tetrahedral cadges smaller than UiO-66-BDC. Zr-Fumarate MOF has a very high potential in natural gas dehydration, adsorption cooling, and toxic gas capture.
- Synthesis 12 1.025 gm of ZrCl 4 ; 0.511 gm of Fumaric acid and 2.515 ml of acetic acid were mixed in 15.31 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 130 °C. Figure 8 shows the PXRD and TGA of the product.
- Synthesis 13 1.025 gm of ZrCl 4 ; 0.511 gm of Fumaric acid and 7.545 ml of acetic acid were mixed in 15.31 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 130 °C.
- Figure 9 shows the PXRD, TGA, SEM and nitrogen sorption isotherm of the product.
- Synthesis 21 1.967 gm of Zr(acac) 4 ; 0.511 gm of Fumaric acid and 7.545 ml of acetic acid were mixed in 15.31 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 130 °C. Figure 10 show the PXRD, TGA, SEM and nitrogen sorption isotherm of the product.
- MOF-808 ( Figure 11) is a three dimensional framework and contains Zr 6 cluster connected by tritopic 1,3, 5-benzene tricarboxylic acid (BTC) linker. Each cluster is coordinated by six BTC linker and six formate ligands.
- MOF-808 contains tetrahedral cages of pore diameter 4.8 A and large adamantine cages of pore diameter 18.4 A.
- the published procedure for preparing this MOF is a very dilute synthesis using excess of DMF and formic acid. With the process of invention we have not only replaced DMF by GVL but also reduced the solvent in the synthesis by 83%.
- UiO-67-BNDC is a isostructural to UiO-67 MOP with 1,1 -binaphthyl-4,4- dicarboxylic acid as a linker.
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Abstract
There is provided a process for preparing a metal organic framework (MOF), comprising the steps (i) preparing a reaction mixture comprising a metal salt and at least one organic linker compound in gamma-valerolactone (GVL)solvent; and(ii) heating the reaction mixture from step (i).
Description
PROCESS FOR PREPARING A MOF WITH GAMMA-VALEROLACTONE
Field of the Invention
The present invention relates to a process for preparing metal organic frameworks (MOFs), in particular to a process for preparing Zr-MOFs. Specifically, the process employs gamma- Valero lactone (GVL) as a solvent. The invention also relates to MOFs produced by such processes.
Background
MOFs or "metal organic frameworks" are compounds having a lattice structure having vertices or "cornerstones" which are metal-based inorganic groups, for example metal oxides, linked together by organic linkers. The linkers are usually at least bidentate ligands which coordinate to the metal-based inorganic groups via functional groups such as carboxylate and/or amine. The porous nature of MOFs renders them promising materials for many applications such as gas storage and catalyst materials.
Perhaps the best known MOF is MOF-5 in which each Z114O cornerstone is coordinated by six bis-carboxylate organic linkers. Other MOFs in which the inorganic cornerstone is for example chromium, copper, vanadium, cadmium or iron are also known.
Numerous processes are known in the prior art for the production of MOFs. The most commonly used techniques involve the reaction of a metal salt with the desired organic linker in a suitable solvent, usually organic, such as
dimethylformamide (DMF). High pressures and temperatures are commonly required to facilitate the reaction. Typical methods are disclosed in, for example, WO 2009/133366, WO 2007/023134, W02007/090809 and WO 2007/118841.
The use of elevated temperatures and pressures not only increases the cost of the process but also means that scale-up to an industrial level poses many
challenges. Apparatus suitable for withstanding the severe reaction conditions is often only compatible with small scale batch synthesis, rather than the continuous
processes favoured for large scale production. Employing high pressures also carries with it safety concerns, particularly when combined with the use of corrosive liquids. Moreover, the use of organic solvents as the reaction medium is undesirable as such solvents are harmful to the environment and are expensive.
As a result of these drawbacks, replacement of the organic solvent with an aqueous medium has been investigated and is reported in, for example, US 7411081 and US 8524932. However, many MOFs are still being prepared in organic solvents because of the very low solubility of many organic linkers in aqueous media. This necessitates the use of solvents which are expensive and harmful to the environment.
Synthesis methods using Dimethylformamide (DMF), Dimethyl sulfoxide (DMSO), and Dimethylamide (DMA) are reported in the literature. DMF and DMA are toxic and their high exposure is considered to be dangerous to life or health. DMSO is a non-toxic solvent but it can be easily decomposed by acids at lower than boiling point temperature, possibly leading to an explosion. Moreover, DMSO upon decomposition will produce dimethyl sulfide, which is highly flammable. Therefore, high volume industrial production using solvents like DMF, DMSO, and DMA is unfeasible and of high health and environmental concern.
As MOFs become increasingly employed as alternatives to, for example, zeolites, polymers and activated carbons there is a need for the development of novel processes for their production which are applicable to use on an industrial scale. The process should ideally be one which is“green” and thus considered environmentally friendly. It should preferably provide high volume MOF production per volume of solvent used. It would also be advantageous to have a process with easier waste management by biodegradation, incineration etc. Ideally, a process which offers improvement in more than one of the above aspects would be developed.
The present inventors have surprisingly found that MOFs may be prepared in a straightforward process utilising gamma- valero lactone (GVF) as a solvent. The procedure is applicable to use on an industrial scale and offers an environmentally friendly and cheap route to these valuable materials.
Gamma- Valero lactone (GVF - structure shown in figure 1) is a colourless organic liquid and has been identified as a potential green solvent. It is readily
obtained from cellulosic biomass. It can be produced at a price between 1-2 US$/L. GVL boils at 207 °C and has a flash point of 96 °C which are both higher than for DMF (B.P. 150 °C and flash point 67 °C ) thereby rendering it easier to operate at high temperature. GVL is chemically and thermally more stable than the organic solvents (such as DMF, DMA and DMSO) usually employed in MOF synthesis. The higher stability of GVL may allow for solvent recycling in MOF production processes.
GVL is also considered as a potential fuel, therefore the solvent waste may be used as a fuel to produce energy thus making the overall processes more economical. GVL upon burning will produce C02 while DMF and DMSO will produce toxic nitrogen and sulfur-containing compounds. Alternatively, because of the high solubility of GVL in water, biodegradation could be pursued to manage the waste.
Summary of the Invention
Thus, in a first aspect, the invention provides a process for preparing a metal organic framework (MOF), comprising the steps:
(i) preparing a reaction mixture comprising a metal salt and at least one organic linker compound in gamma- valero lactone (GVL) solvent; and
(ii) heating the reaction mixture from step (i).
In a particularly preferable embodiment, the metal organic framework is a zirconium-based metal organic framework (Zr-MOF).
In a further aspect, the invention provides a metal organic framework (MOF) produced or formable by the processes as herein described.
Detailed Description
The present invention describes a process for the preparation of a metal organic framework (MOF), such as a zirconium-based metal organic framework (Zr-MOF). The process involves preparing a reaction mixture comprising a metal
salt and at least one organic linker compound in gamma- valerolactone (GVL) solvent and heating the reaction mixture. The process typically involves
subsequently isolating the MOF. MOF
As used herein, the term“MOF” is intended to cover any metal organic framework. MOFs typically comprise at least one metal ion or cluster of metal ions and at least one organic linker compound.
The metal ion or cluster of metal ions may be any suitable metal selected from Groups 1 to 16 of the Periodic Table. The metal ion may have any valence appropriate for the specific metal. 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, lr, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg) and post-transition metals (Al, Ga, In, Tl, 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 metal ion is selected from the group consisting of Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Al, Zr, Gd, Eu, Tb, Ce, Y, Hf, and mixtures thereof.
In a particularly preferable embodiment, the metal ion is selected from the group consisting of, zirconium, magnesium, zinc, aluminium, iron, cerium, hafnium and yttrium. Most preferably, the metal ion is zirconium.
Whilst it is possible for a mixture of metal ions to be used, it is preferable if the MOF contains only a single type of metal ion.
In a particularly preferred embodiment, the process of the invention is used to prepare zirconium-based metal organic frameworks (Zr-MOFs). As used herein, the term“Zr-MOF” is intended to cover any metal organic frameworks (MOFs) which comprise at least one zirconium metal ion. The Zr-MOFs of the invention have“cornerstones” which are zirconium inorganic groups. Typical zirconium
inorganic groups include zirconium ions connected by bridging oxygen or hydroxide groups. These inorganic groups are further coordinated to at least one organic linker compound. In some cases, the inorganic groups may be further connected to non bridging modulator species, complexing reagents or ligands (e.g. sulfates or carboxylates such as formate, benzoate or acetate) and/or solvent molecules. The zirconium oxide unit is usually based on an idealized octahedron of Zr-ions which are p3-bridged by O2 and/or OH ions via the faces of the octahedron and further saturated by coordinating moieties containing O-atoms like carboxylate groups. The idealised Zr oxide cluster is considered to be a Zr6032-cluster which comprises between 6 and 12 (preferentially as close as possible to 12) carboxylate groups. However, in practice, there is a degree of flexibility in the structure of the cluster. The cluster may be represented by the formula Zr6Ox(OH)8-x wherein x is in the range 0 to 8. For example, the cluster may be represented by the formula
Zr6(0)4(0H)4,
Whilst it not outside the bounds of the present invention for the Zr-MOF to comprise additional metal ions other than zirconium, such as hafnium, titanium, or cerium, zirconium may be the only metal ion present. If additional metal ions are present these may be present in an amount of up 50 wt% relative to total amount of metal ions, preferably up to 25 wt%, more preferably up to 10 wt%, e.g. up to 5 wt%.
The Zr-MOFs of the invention particularly preferably have cornerstones having at least 12 coordination sites for the organic linkers, e.g. 12-36, especially preferably at least 14, 16 or 18, most especially 24. In this way at least 6, more preferably at least 8, especially at least 12 bidentate ligand groups of the organic linkers can bind to each cornerstone.
In another preferred embodiment the Zr-MOF of the invention particularly preferably has cornerstones having at least 6 coordination sites for the organic linkers, e.g. 6-36, especially preferably at least 6, 12, 18, most especially 24. In this way at least 6, more preferably at least 8, especially at least 12 bidentate or at least 6 tridentate or hexadentate ligand group of the organic linkers can bind to each cornerstone.
The structure of the MOFs of the invention may be one- two- or three- dimensional. The MOF usually comprises pores which are present in the voids between the coordinated network of zirconium ions and organic linker compounds. The pores are typically micropores, having a diameter of 2 nm or less, or mesopores, having a diameter of 2 to 50 nm.
In all embodiments, the surface area of the MOF is preferably at least 400 m2/g, more preferably at least 500 m2/g, especially at least 700 m2/g, such as at least 1020 m2/g, for example at least 1050 m2/g, e.g. at least 1200 m2/g, as measured by nitrogen adsorption at 77 K, using BET method. The surface area may be up to 10000 m2/g, especially up to 5000 m2/g. It will be understood that, where functionalised organic linker compounds are used, the presence of additional, and often bulky, groups may affect (i.e. reduce) the surface area of the MOF.
In addition to the at least one metal ion or cluster of metal ions, the MOFs of the invention comprise at least one organic linker compound. The organic linker compound is typically at least bidentate, i.e. has at least two functional groups capable of coordinating to the metal ion. The organic linker compound may also be tridentate (i.e. containing three functional groups) or tetradentate (i.e. containing four functional groups). In one embodiment, the organic linker 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 MOF may have a metal ion to organic linker molecule ratio of from 1 :0.30 to 1 :0.55, especially 1 :0.33 to 1 :0.51, particularly 1 :0.33. Other preferred metal ion to organic linker molecule ratios are 0.5: 1, 1 : 1, 3: 1 and 1 :3, especially 1 : 1.
The organic linker compounds of the MOFs of the invention may be any organic linker molecule or molecule combination capable of binding to at least two inorganic cornerstones and comprising an organic moiety. By“organic” moiety we mean a carbon based group which comprises at least one C-H bond and which may optionally comprise one or more heteroatoms such as N, O, S, B, P, Si. Typically, the organic moiety will contain 1 to 50 carbon atoms.
The organic linker compound may be any of the linkers conventionally used in MOF production. These are generally compounds with at least two cornerstone
binding groups, e.g. carboxylates, optionally with extra functional groups which do not bind the cornerstones but may bind metal ions on other materials it is desired to load into the MOF. The introduction of such extra functionalities is known in the art and is described for example by Campbell in JACS 82:3126-3128 (1960).
The organic linker compound may be in the form of the compound itself or a salt thereof, e.g. a disodium 1 ,4-benzenedicarboxylate salt or a monosodium 2- sulfoterephthalate salt.
The organic linker compound is preferably soluble in the GVL solvent employed in the processes of the invention. By“soluble” we mean that it preferably has a solubility which is high enough to enable the formation of a homogenous solution. The solubility of the organic linker compound in GVL may be at least 1 g/L at room temperature and pressure (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
The organic linker compound typically comprises at least two functional groups capable of binding to the inorganic cornerstone. By“binding” we mean linking to the inorganic cornerstone by donation of electrons (e.g. an electron pair) from the linker to the cornerstone. Preferably, the linker comprises two, three or four functional groups capable of such binding.
Non-limiting functional groups that can be contained by the organic ligand to form a MOF according to the invention are -COOH, -CSSH, -N02, - B(OH)2, - S03H, -Ge(OH)3, -Sn(OH)3, -Si(SH)4, -Ge(SH)4, -Sn (SH)3, -P03H, - As03H, - AS04H, -P(SH)3, AS(SH)3, C4H204, -RSH, -RNH2, -RNR-, -ROH, - RCN, - PO(OR)2, -RN3, where R is hydrogen, alkyl, alkylene, preferably Cl, C2, C3, C4 or C5 alkylene, or aryl group, preferably comprising 1 or 2 aromatic nuclei. Typically, the organic linker comprises at least two functional groups selected from the group of carboxylate (COOH), amine (NH2), nitro (N02), anhydride and hydroxyl (OH) or a mixture thereof. In a preferable embodiment, the linker comprises two, three or four carboxylate groups.
The organic linker compound may be based on a saturated or unsaturated aliphatic compound or an aromatic compound. Alternatively, the organic linker compound may contain both aromatic and aliphatic moieties.
In one embodiment, the aliphatic organic linker compound may comprise a linear or branched Ci_2o alkyl group or a C3_i2 cycloalkyl group. The term "alkyl" is intended to cover linear or branched alkyl groups such as all isomers of propyl, butyl, pentyl and hexyl. In all embodiments, the alkyl group is preferably linear. Particularly preferred cycloalkyl groups include cyclopentyl and cyclohexyl.
In one preferred embodiment, the organic linker compound comprises an aromatic moiety. The aromatic moiety can have one or more aromatic rings, for example two, three, four or five rings, with the rings being able to be present separately from one another and/or at least two rings being able to be present in condensed form. The aromatic moiety particularly preferably has one, two or three rings, with one or two rings being particularly preferred, most preferably one ring. Each ring of said moiety can independently comprise at least one heteroatom such as N, O, S, B, P, Si, preferably N, O and/or S.
The aromatic moiety preferably comprises one or two aromatic C6 rings, with the two rings being present either separately or in condensed form. Particularly preferred aromatic moieties are benzene, naphthalene, biphenyl, bipyridyl and pyridyl, especially benzene.
Examples of suitable organic linker compounds include oxalic acid, ethyloxalic acid, fumaric acid, 1,3, 5-benzene tricarboxylic acid (BTC), 1,1’- binaphthyl 4,4'-dicarboxylic acid (BINAP-H2), 1,3, 5-benzene tribenzoic acid (BTB), benzene tribiphenylcarboxylic acid (BBC), 5, 15-bis (4-carboxyphenyl) zinc (II) porphyrin (BCPP), 1, 4-benzene dicarboxylic acid (BDC), 2-amino- 1, 4-benzene dicarboxylic acid (R3-BDC or H2N BDC), 1,2, 4, 5-benzene tetracarboxylic acid, 2- nitro-l, 4-benzene dicarboxylic acid l,l'-azo-diphenyl 4,4'-dicarboxylic acid, eye lo butyl- 1, 4-benzene dicarboxylic acid (R6-BDC), 1,2, 4-benzene tricarboxylic acid, 2,6-naphthalene dicarboxylic acid (NDC), l,l'-biphenyl 4,4'-dicarboxylic acid (BPDC), 2,2'-bipyridyl-5,5'-dicarboxylic acid, adamantane tetracaboxylic acid (ATC), adamantane dibenzoic acid (ADB), adamantane teracarboxylic acid (ATC), dihydroxyterephthalic acid (DHBDC), biphenyltetracarboxylic acid (BPTC), tetrahydropyrene 2,7-dicarboxylic acid (HPDC), pyrene 2,7-dicarboxylic acid (PDC), pyrazine dicarboxylic acid, acetylene dicarboxylic acid (ADC), camphor dicarboxylic acid, benzene tetracarboxylic acid, l,4-bis(4-carboxyphenyl)butadiyne,
nicotinic acid, and terphenyl dicarboxylic acid (TPDC). Other acids besides carboxylic acids, e.g. boronic acids may also be used. Anhydrides may also be used.
In a particularly preferred embodiment, the organic linker compound is selected from the group consisting of 1 ,4-benzene dicarboxylic acid (BDC), fumaric acid, 1,3, 5-benzene tricarboxylic acid (BTC), 1 , G-binaphthyl 4,4'-dicarboxylic acid (BINAP-H2) or mixtures thereof.
A mixture of two or more of the above-mentioned linkers may be used. It is preferable, however, if only one type of linker is used.
Where the MOF is a Zr-MOF with a bidentate organic linker it is preferably of UiO-66 type. UiO-66 type Zr-MOFs cover structures in which the zirconium inorganic groups are Zr6(0)4(0H)4 and the organic linker compound is 1 ,4-benzene dicarboxylic acid or a derivative thereof. Derivatives of 1 ,4-benzene dicarboxylic acid used in UiO-66 type Zr-MOFs include 2-amino- 1, 4-benzene dicarboxylic acid, 2 -nitro-l, 4-benzene dicarboxylic acid, 1,2, 4-benzene tricarboxylic acid and 1,2, 4,5- benzene tetracarboxylic acid.
When the linker is 1 ,4-benzene dicarboxylic acid, the resulting MOF may be referred to as UiO-66(Zr). When the linker is 2-amino- 1, 4-benzene dicarboxylic acid, the resulting MOF may be referred to as UiO-66(Zr)-NH2. When the linker is 1,2, 4-benzene tricarboxylic acid, the resulting MOF may be referred to as UiO- 66(Zr)-COOH. When the linker is 1,2, 4, 5-benzene tetracarboxylic acid, the resulting MOF may be referred to as UiO-66(Zr)-2COOH.
Where the MOF is a Zr-MOF with a tridentate organic linker it is preferably of MOF-8O8 type. Where the MOF is a Zr-MOF with, tetradentate or hexadentate organic linker it is preferably of NU- 1000, pbz-MOF-l type structure respectively.
A mixture of linkers may be used to introduce one or more functional groups within the pore space, e.g. by using aminobenzoic acid to provide free amine groups or by using a shorter linker such as oxalic acid. This introduction of functionalised linkers is facilitated by having a MOF with inorganic cornerstones with a high number of coordination sites. Where the number of these coordination sites exceed the number required to form the stable 3D MOF structure, functionalisation of the organic linkers may be effected, e.g. to carry catalytic sites, without seriously weakening the MOF structure.
By“functionalised MOF” we mean a MOF wherein one or more of the backbone atoms of the organic linkers carries a pendant functional group or itself forms a functional group. Functional groups are typically groups capable of reacting with compounds entering the MOF or acting as catalytic sites for reaction of compounds entering the MOF. Suitable functional groups will be apparent to a person skilled in the art and in preferred embodiments of the invention include amino, nitro, thiol, oxyacid, halo (e.g. chloro, bromo, fluoro) and cyano groups or heterocyclic groups (e.g. pyridine), each optionally linked by a linker group, such as carbonyl. The functional group may also be a phosphorus-or sulfur-containing acid.
A particularly preferred functional group is halo, most preferably a fluoro group.
Preferably, the functionalised MOF has a surface area of at least 400 m2/g, more preferably at least 500 m2/g, especially at least 700 m2/g, such as at least 1020 m2/g.
Process
The process of the invention comprises at least the steps of:
(i) preparing a reaction mixture comprising a metal salt and at least one organic linker compound in gamma- valero lactone (GVL) solvent; and
(ii) heating the reaction mixture from step (i).
The organic linker compound may be any organic linker as hereinbefore defined. It will be understood that the organic linker described in the context of the MOF produced by the processes of the invention is the same organic linker which is used as a starting material in step (i) of the process of the invention, albeit that once bound to the inorganic cornerstone the organic linker will be deprotonated. Thus all preferable embodiments defined above relating to the organic linker in the context of the MOF apply equally to this compound as a starting material.
The metal ions of the MOF are provided in the form of at least one metal salt, which may or may not be in its hydrated form. Whilst the use of a mixture of
two or more different salts is encompassed by the invention, it is preferable if one salt is used.
The metal salt is usually soluble in GVL, i.e. preferably having a solubility of at least 1 g/L at room temperature (i.e. 18 to 30 °C) and pressure (i.e. 0.5 to 3 bar) (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
Preferable metal ions are discussed above in the context of the MOF and all embodiments discussed therein apply equally here. Suitable counter-ions will be familiar to the skilled worker and may include halides (e.g. chlorides and bromides), acetates, nitrates, formats, oxalates, acetylacetonates, carbonates, tatrates, oxides, acrylates, carboxylates, sulfates, hydroxides, perchlorates, oxynitrates and oxychlorides.
Where the metal salt is a zirconium salt, examples of preferable metal salts include zirconium sulfate, zirconium hydroxide, zirconium acetylacetonate, zirconium chloride (ZrCl4) and zirconyl chloride (ZrOCf nFLO, wherein n is an integer from 1 to 10, preferably 8).
In some embodiments, the reaction mixture preferably further comprises a growth modulator. By“growth modulator” we mean a compound that affects the rate of crystal growth, making it slower or faster. Suitable growth modulators are known in the art. Non-limiting examples of growth modulator compounds for use in the invention are monocarboxylic acids compounds (such as acetic acid, benzoic acid, formic acid, trifluroacetic acid or amino acids), inorganic acids (such as hydrochloric acids, hydrofluoric acid, sulfuric acids). Basic compounds such as alkali hydroxide (e.g. NaOH or KOH) or ammonium hydroxide could also be used as a growth modulator
The reaction mixture prepared in step (i) of the processes of the invention is typically prepared by mixing the various components together in the GVL solvent. Mixing may be carried out by any known method in the art, e.g. mechanical stirring. The mixing is preferably carried out at temperature between 18 and 50 °C. Usually, step (i) is carried out at or around atmospheric pressure, i.e. 0.5 to 2 bar, especially 1 bar.
In step (ii) of the process, the reaction mixture prepared in step (i) is heated. Heating is usually carried out to a temperature at which the reaction mixture boils.
Preferably, the temperature is increased to 50 - 150 °C, more preferably 60 - 130 °C, such as 80-120 °C. Usually, step (ii) is carried out at or around atmospheric pressure, i.e. 0.5 to 2 bar, especially 1 bar.
The reaction mixture is preferably heated for a period of time of at least 20 minutes, more preferably at least 30 minutes, even more preferably at least 50 minutes, i.e. at least 60 minutes. The reaction mixture is preferably heated for not more than 10 hours, more preferably not more than 5 hours, especially not more than 2 hours.
Step (ii) is generally carried out by heating the reaction mixture from step (i) under reflux at the temperature and for the time periods as hereinbefore defined.
The skilled man will appreciate that heating under reflux is a routine procedure with which anyone working in the field of the invention would be familiar.
The method of heating may be by any known method in the art, such as heating in a conventional oven, a microwave oven or heating in an oil bath.
The high boiling point (207 °C) and high flash point (97 °C) of GVL offers numerous advantages over those of previous methods wherein DMF, DMSO and DMA solvents were used as the reaction medium. The mild reactions conditions and high stability of the solvent used in the process of the invention offer the possibility of solvent recycling. GVL is also considered as a potential fuel; therefore the solvent waste can be used as a fuel to produce energy thus making the overall processes more economical. GVL upon burning will produce C02 while DMF and DMSO will produce toxic nitrogen and sulfur-containing compounds. Alternatively, because of the high solubility of GVL in water, biodegradation can be pursued to manage the waste. This offers improvements in terms of costs, safety and suitability for industrial scale-up.
The molar ratio of total metal ions to total organic linker compound(s) present in the reaction mixture prepared in step (i) is typically between 1 :0.30 and 1 :1, however in some embodiments an excess of the organic linker compound may be used. Thus, in some embodiments, the molar ratio of total metal ions to total organic linker compound(s) in the reaction mixture is in the range 1 : 0.30 to 1 :5, such as 1 :1 or 1 :4.
It will be appreciated that the MOF product forms during step (ii) of the process.
The processes of the invention usually comprise a further step (iii) isolating the MOF.
Advantageously, the MOF is usually formed as a crystalline product which can be isolated quickly and simply by methods such as filtration, or centrifugation. This offers an improvement over some methods of the prior art which produce an amorphous or gel-like product which must be further recrystallized before it can be isolated. The processes of the present invention thus preferably eliminate the need for these additional steps.
The isolation step (iii) is typically carried out by filtration, but isolation may also be performed by processes such as centrifugation, solid-liquid separations or extraction. After isolation, the MOF is preferably obtained as a fine crystalline powder having crystal size of 0.1 to 100 pm, such as 10 to 50 pm.
In addition to steps (i), (ii) and (iii), the processes of the invention may comprise additional steps, such as drying and/or cooling. Typically, there will be a cooling step between steps (ii) and (iii). Cooling usually involves bringing the temperature of the reaction mixture back to room temperature, i.e. 18-30 °C.
In a further embodiment, the invention relates to a metal organic framework (MOF) produced or formable by the processes as herein described.
Applications
The MOF produced or formable by the processes of the present invention may be employed in any known application for such materials. Applications therefore include, but are not restricted to, electrode materials, drug reservoirs, catalyst materials, adsorbents and cooling media.
Figures
Figure 1: Drawing of molecular structure of gamma- valero lactone (GYL).
Figure 2. Structure of UiO-66-BDC.
Figure 3a-b. Powder X-ray diffraction patterns of the UiO-66-BDC product from the synthesis 1-11.
Figure 4. Powder X-ray diffraction pattern, Thermogravimetric analysis, nitrogen sorption and Scanning electron microscopy of UiO-66-BDC obtained in upscale synthesis 10. Figure 5. Powder X-ray diffraction pattern, Thermogravimetric analysis, nitrogen sorption and Scanning electron microscopy of UiO-66-BDC obtained in upscale synthesis 11.
Figure 6. Structure of Zr-Fumarate.
Figure 7a-b. Powder X-ray diffraction patterns of the UiO-66-BDC product from the syntheses 12-21
Figure 8. Powder X-ray diffraction pattern and Thermogravimetric analysis of Zr- Fumarate obtained from upscaled synthesis 12.
Figure 9. Powder X-ray diffraction pattern, Thermogravimetric analysis, nitrogen sorption isptherm and scanning electron microscopy of Zr-Fumarate obtained in upscale synthesis 13.
Figure 10. Powder X-ray diffraction pattern, Thermogravimetric analysis, nitrogen sorption isotherm and scanning electron microscopy of Zr-Fumarate obtained in upscale synthesis 21.
Figure 11. Structure of MOF-808.
Figure 12. Powder X-ray diffraction pattern and Thermogravimetric analysis of MOF-808 obtained by process of invention.
Figure 13. Powder X-ray diffraction pattern of UiO-67-BINAP obtained by process of invention.
Examples
Techniques
Surface Area measurement
The specific surface area was determined by means of N2 physisorption measured on a Belsorp-mini apparatus at 77 K. Prior to the measurement the sample was activated at 423 K under vacuum for 3 h to remove occluded water molecules. The surface area was calculated by the BET-method (DIN 66131) and the Langmuir method (DIN 66135).
X-ray crystallography
All powder X-ray diffraction patterns were collected on a Bruker D8 Discovery diffractometer equipped with a focusing Ge-monochromator, using Cu-Ka radiation(xx=l.54l8 A) and Bruker LYNXEYE detector. Patterns were collected in reflectance Bragg-Brentano geometry in the 2 Q range from 2 to 50°.
Thermogravimetric analysis
Measurements were made with a Stanton Redcroft TGA-DSC, in which ca. 30 mg of powdered sample was loaded inside a platinum crucible. Samples were heated to 900 °C at a rate of 5 °C per minute while exposed to a continuous flow of both N2 (20 mL/min) and 02 (5 mL/min).
Scanning electron microscopy (SEM)
An ultrahigh resolution scanning electron microscope Hitachi SU8230 with a cold cathode field emission type electron gun was used to obtained high resolution images of the materials.
UiO-66-BDC (Figure 2) is a prototype MOF of UiO-66 series with hexanuclear Zr6 cluster as a inorganic comer stone connected by Benzene- 1 ,4-dicarboxylic acid (BDC-H2) as an organic linker. This is one of the most thermally and chemically stable MOF. It contains octahedral and tetrahedral cadges accessible via triangular window. We have found several conditions using: ZrCl4, Zr0CL2.8H20, and Zr(acac)4 (acac: acetylacetonate) as a zirconium source, with and without Formic acid and acetic acid as a modulator.
A synthesis screening was performed with the metal: linker: solvent molar ratio set to 1 : 1 :52 respectively while changing the modulator type (acetic acid, formic acid) and modulator amount (0, 10, 20, 30). The reaction mixture was transfer in glass vial and heated at 120 °C inside heating oven. The details of the reagent amount are given in a Table 1. The final product was separated by centrifugation and washed with GVL once at room temperature before drying at 100 °C. The process provides a space time yield of 250-334 kg/ m3 day. Figure 3a and b show the PXRD patterns of the obtained products.
Synthesis 10 and 11 - Scale up to gm scale:
Synthesis 10: 1.161 gm of Zr0Cl2.8H20; 0.599 gm of 1 ,4-benzenedicarboxylic acid and 4.078 ml of formic acid were mixed in 17.95 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 150 °C. Figure 4 shows the PXRD, TGA, SEM and nitrogen sorption isotherm of the product calcined at 270 °C.
Synthesis 11: 1.756 gm of Zr(acac)4; 0.599 gm of 1 ,4-benzenedicarboxylic acid and 1.359 ml of formic acid were mixed in 17.95 ml of GVL solution in round bottom
flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 150 °C. Figure 5 shows the PXRD, TGA, SEM and nitrogen sorption isotherm of the product calcined at 270 °C. Table 1. Reagents quantities used to screen for the synthesis of UiO-66-BDC.
Zr-Fumarate (Figure 6) also contains hexanuclear Zr6 cluster as an inorganic comer stone but they are connected by Fumarate(FA). Fumaric acid is shorter linker than Benzene- 1 ,4-dicarboxylic acid therefore Zr-Fumarate contains octahedral and tetrahedral cadges smaller than UiO-66-BDC. Zr-Fumarate MOF has a very high potential in natural gas dehydration, adsorption cooling, and toxic gas capture. We have found several conditions using ZrCl4, Zr0CL2.8H20, and Zr(acac)4 as a zirconium source, with and without Formic acid and acetic acid as a modulator. A synthesis screening was performed with the metal: linker: solvent molar ratio set to 1 :1 :37 respectively while changing the modulator type (acetic acid, formic acid) and modulator amount (0, 10, 20, 30). The reaction mixture was transfer in glass vial and heated at 120 °C inside heating oven. The details of the reagent amount are
given in a Table 2. The final product was separated by centrifugation and washed with GVL ones at room temperature before drying at 100 °C. The process provide space time yield of 340-391 kg/ m3 day. Figure 7 a and b show the PXRD of the products.
Scale up synthesis 12,13 and 21 to gm scale:
Synthesis 12: 1.025 gm of ZrCl4; 0.511 gm of Fumaric acid and 2.515 ml of acetic acid were mixed in 15.31 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 130 °C. Figure 8 shows the PXRD and TGA of the product.
Synthesis 13: 1.025 gm of ZrCl4; 0.511 gm of Fumaric acid and 7.545 ml of acetic acid were mixed in 15.31 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 130 °C. Figure 9 shows the PXRD, TGA, SEM and nitrogen sorption isotherm of the product.
Synthesis 21: 1.967 gm of Zr(acac)4; 0.511 gm of Fumaric acid and 7.545 ml of acetic acid were mixed in 15.31 ml of GVL solution in round bottom flask. The reaction mixture was refluxed at 120 °C. The product was separated by filtration and washed with GVL before drying at 130 °C. Figure 10 show the PXRD, TGA, SEM and nitrogen sorption isotherm of the product.
Table 2. Reagents quantities used to screen for the synthesis of Zr-Fumarate.
MOF-808 (Figure 11) is a three dimensional framework and contains Zr6 cluster connected by tritopic 1,3, 5-benzene tricarboxylic acid (BTC) linker. Each cluster is coordinated by six BTC linker and six formate ligands. MOF-808 contains tetrahedral cages of pore diameter 4.8 A and large adamantine cages of pore diameter 18.4 A. The published procedure for preparing this MOF is a very dilute synthesis using excess of DMF and formic acid. With the process of invention we have not only replaced DMF by GVL but also reduced the solvent in the synthesis by 83%.
83 mg ofZrCU; 25 mg of 1,3,5- benzene tricarboxyl acid (BTC-H2) and 0.673 ml of acetic acid were mixed in 1.138 ml of GVL solution in glass vial. The reaction mixture was heated at 120 °C. The product was separated by filtration and washed with GVL before drying at 150 °C. Ligure 12 shows the PXRD, and TGA, of the product calcined at 200 °C
UiO-67 -BINAP (BINAP: L G-binaphthyl 4,4'-dicarboxylic acid)
UiO-67-BNDC is a isostructural to UiO-67 MOP with 1,1 -binaphthyl-4,4- dicarboxylic acid as a linker. We have prepared this MOP in GVL with amino acid as a modulator.
87 mg ofZrCU; 127 mg of 1 , G-binaphthyl 4,4'-dicarboxylic acid (BINAP-Fp) and 2l4mg of L-Proline, 0.0013 ml cone. HCL were mixed in 10.23 ml of GVL solution in glass vial. The reaction mixture was heated at 120 °C. The product was separated by centrifugation and washed with GVL before drying at 130 °C. Ligure 13 shows the PXRD, of the final product.
Claims
1. A process for preparing a metal organic framework (MOF), comprising the steps:
(i) preparing a reaction mixture comprising a metal salt and at least one organic linker compound in gamma- valero lactone (GVL) solvent; and
(ii) heating the reaction mixture from step (i).
2. A process as claimed in claim 1, wherein the metal salt comprises a metal ion selected from the group consisting of, zirconium, magnesium, zinc, aluminium, iron, cerium, hafnium and yttrium, preferably zirconium.
3. A process as claimed in claim 1 or 2, wherein the metal salt(s) is selected from the group consisting of zirconium sulfate, zirconium hydroxide, zirconium acetylacetonate, zirconium chloride (ZrC’f) and zirconyl chloride (ZrOCf nFTO, wherein n is an integer from 1 to 10, preferably 8).
4. A process as claimed in any of claims 1 to 3, wherein the at least one organic linker compound comprises at least two functional groups selected from the group consisting of carboxylate (COOH), amine (NH2), anhydride and hydroxyl (OH) or a mixture thereof.
5. A process as claimed in any of claims 1 to 4, wherein the at least one organic linker compound comprises a linear or branched Ci_2o alkyl group, a C3-i2 cycloalkyl group and/or an aromatic moiety, preferably an aromatic moiety such as benzene, naphthalene, biphenyl, bipyridyl or pyridyl.
6. A process as claimed in any of claims 1 to 5, wherein the organic linker compound is selected from the group consisting of 1 ,4-benzene dicarboxylic acid (BDC), fumaric acid, 1,3, 5-benzene tricarboxylic acid (BTC), 1,1’- binaphthyl 4,4'-dicarboxylic acid (BINAP-H2) or mixtures thereof.
7. A process as claimed in any of claims 1 to 6, wherein the reaction mixture in step (i) further comprises a growth modulator.
8. A process as claimed in claim 7, wherein said growth modulator is selected from the group consisting of monocarboxylic acids and inorganic acids.
9. A process as claimed in any of claims 1 to 8, wherein step (i) is carried out at a temperature between 18 and 50 °C.
10. A process as claimed in any of claims 1 to 9, wherein step (i) is carried out at or around atmospheric pressure, preferably 0.5 to 2 bar.
11. A process as claimed in any of claims 1 to 10 wherein in step (ii) of the
process, the reaction mixture from step (i) is heated to a temperature in the range 50 - 150 °C.
12. A process as claimed in any of claims 1 to 11, wherein step (ii) is performed for a time period of at least 20 minutes.
13. A process as claimed in any of claims 1 to 12, wherein the MOF is produced as a crystalline powder.
14. A metal organic framework (MOF) produced by the process as defined in any of claims 1 to 13.
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US20240213533A1 (en) * | 2018-12-07 | 2024-06-27 | Jinhua Chenyang Technology Co., Ltd. | Additive for low temperature lithium ion battery, and electrolyte and lithium ion battery using same |
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