CN107774329A - A kind of metal-organic framework materials and preparation method thereof - Google Patents
A kind of metal-organic framework materials and preparation method thereof Download PDFInfo
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- CN107774329A CN107774329A CN201610736797.0A CN201610736797A CN107774329A CN 107774329 A CN107774329 A CN 107774329A CN 201610736797 A CN201610736797 A CN 201610736797A CN 107774329 A CN107774329 A CN 107774329A
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- metal
- organic framework
- framework materials
- solvent
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- 239000000463 material Substances 0.000 title claims abstract description 105
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical class OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000002184 metal Chemical class 0.000 claims abstract description 14
- 230000000630 rising effect Effects 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- -1 nitrogen-containing compound Chemical class 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 4
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical class CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 claims description 4
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical class CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-butylamine Natural products CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical class CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 19
- 239000013384 organic framework Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000010953 base metal Substances 0.000 description 14
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 12
- 230000009102 absorption Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000013148 Cu-BTC MOF Substances 0.000 description 4
- 239000013147 Cu3(BTC)2 Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 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 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 3
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000013151 Basolite® C 300 Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Abstract
The invention discloses a kind of metal-organic framework materials and preparation method thereof.This method includes：（1）By thick 1,3,5 benzenetricarboxylic acids are added in the first solvent and recrystallized, 1 after being purified, 3,5 benzenetricarboxylic acids, the step of recrystallization includes rising temperature for dissolving, cooling separates out, surfactant is introduced wherein before thick 1,3,5 benzenetricarboxylic acid rising temperature for dissolving, during rising temperature for dissolving and/or after rising temperature for dissolving and before cooling separates out；（2）By 1 after purification, 3,5 benzenetricarboxylic acids, metal salt and the second solvent are well mixed, then crystallization, separation, washing and drying, obtain described metal-organic framework materials.This method is 1,3, surfactant is added in 5 benzenetricarboxylic acid recrystallization processes, not only increase 1, the purity of 3,5 benzenetricarboxylic acids, and a small amount of surfactant can also enter the crystals of recrystallization, so as to avoid reunion of the metal-organic framework materials in building-up process between crystal, the specific surface area and pore volume of metal-organic framework materials are improved.
Description
Technical field
The present invention relates to a kind of metal-organic framework materials and preparation method thereof.
Background technology
Metal-organic framework materials（Metal-Organic Frameworks, abbreviation MOFs）Refer to by oxygen-containing, nitrogen etc.
What multiple tooth organic ligand formed with transition metal ions self assembly, there is the class zeolitic frameworks material of special pore passage structure.They have
Have that porosity is high, specific surface area is big, density is small, aperture structure, the advantages that composition and Functional Design are adjustable, this is deposited to develop height
Storage capacity, the energy gas adsorbent of high shape-selective separating effect and release agent provide opportunity.
Cu3(BTC)2Also referred to as HKUST-1 types metal-organic framework materials, the coordination polymer is by double-core copper bunch and equal benzene
Tricarboxylic acid self assembly forms.It is crystallized in cubic system, belongs to space group Fm-3m.When the removing copper ion combination from skeleton
During water, Cu3(BTC)2The three-dimensional porous structure with ligand unsatuated metal structure will be become, the main pore size of the structure is big
Small is 9, and slightly smaller tetrahedron side pocket size is 5, and passes through tri-angle-holed window and main aperture road phase of the size for 3.5
Even.Just because of Cu3(BTC)2Possessing two kinds of typical holes so that it is not only the excellent material of gas molecule absorption, and
The excellent material of mixed gas separation.
At present, Cu is mainly prepared using hydrothermal synthesis method3(BTC)2Material.Such as the A of CN 102863463 disclose one kind
The method for preparing Cu-BTC and nanometer Cu-BTC, first by Cu (ClO4)2The aqueous solution and 1,3,5- benzenetricarboxylic acids ethanol solution
Prepare synthesis Cu (C9H406)(H2O), then it is immersed under organic solvent or steam ambient, obtains Cu-BTC.
CN102336774A discloses a kind of nano level metal organic bone of Fast back-projection algorithm at room temperature based on trimesic acid
The method of frame nano material.At room temperature, reacted, obtained after the metal acetate aqueous solution is mixed with trimesic acid solution
Metal organic framework nano particle.This method belongs to dynamic synthesis technique and carried out at room temperature, have quick, easy, energy-conservation,
The advantages that yield is high.
CN103920158A discloses a kind of synthetic method of Nanosized metal organic backbone, using surfactant as mould
Plate, using can be provided containing N or O lone electron pair atom rigid ligand as organic ligand, with alkali earth metal, group of the lanthanides gold
It is metal ion to belong to element, transition metal, the ion of one or more kinds of metallic elements in amphotere, use
Hydro-thermal method or microwave method or ultrasonic method are synthesized.
But above-mentioned metal-organic framework materials are used as former in preparation process using the benzenetricarboxylic acid of high-purity 1,3,5-
Material, so as to cause higher production cost, is unfavorable for industrialized popularization.It is used for synthesizing using the relatively low technical grade part of purity
Metal-organic framework materials, its crystallinity is poor, and specific surface area is smaller, greatly reduces the feasibility of its practical application.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of metal-organic framework materials and its preparation
Method.This method with purity than the relatively low benzenetricarboxylic acid of technical grade 1,3,5- for Material synthesis metal-organic framework materials, and make
Metal-organic framework materials not only have very high crystallinity, specific surface area, total pore volume and heat endurance, but also with very
High yield.
A kind of preparation method of metal-organic framework materials provided by the invention, comprises the following steps：
（1）Thick 1,3,5- benzenetricarboxylic acid is added in the first solvent and recrystallized, 1 after being purified, 3,5- benzene front threes
Acid, the recrystallization includes rising temperature for dissolving, cool the step of separating out, wherein before thick 1,3,5- benzenetricarboxylic acid rising temperature for dissolving, rising
Surfactant is introduced in warm course of dissolution and/or after rising temperature for dissolving and before cooling separates out；
（2）By 1 after purification, 3,5- benzenetricarboxylic acids, metal salt and the second solvent are well mixed, then crystallization, separation, washing and
Dry, obtain described metal-organic framework materials.
The surfactant be 1-METHYLPYRROLIDONE, Tween-20, Tween-40, Tween-60, Tween-80, sapn-
20th, the one or more in Arlacel-40, Arlacel-60, Arlacel-80, neopelex, preferably N- crassitudes
Ketone.
First solvent is low-carbon alcohols, preferably the one or more in methanol, ethanol, propyl alcohol, butanol, ethylene glycol,
More preferably ethanol.
Thick 1,3,5- benzenetricarboxylic acids can be with purity than relatively low 1,3,5- benzenetricarboxylic acid, such as the benzene front three of technical grade 1,3,5-
Acid, described thick 1, the purity of 3,5- benzenetricarboxylic acids can be 50wt%~70wt%.
After being purified by the inventive method, 1 after the purification, the purity of 3,5- benzenetricarboxylic acids can be 80.00wt%~
99.99wt%, preferably 90.0wt%~99.9wt%.
The part by weight of the thick 1,3,5- benzenetricarboxylic acids, surfactant and the first solvent is 1:（0.01~0.5）:（1
~50）, preferably 1:（0.02~0.1）:（2~5）.
In step（1）In, the specific steps of the rising temperature for dissolving can be：With 0.5 DEG C/min~10 DEG C/min heating
Speed is increased to 30 DEG C~100 DEG C, and keeps 30min~2h.In step（1）In, the specific steps that the cooling separates out can be with
For：10 DEG C~25 DEG C are cooled to 0.5 DEG C/min~10 DEG C/min rate of temperature fall, and keeps 30min~2h.
In step（1）In, the recrystallization is additionally may included in after cooling separates out, the step that is separated, washed and dried
Suddenly.Separation can select conventional separation method, can be filtering, centrifuge etc., drying condition does not have particular/special requirement, realizes
It drying, can be dried in the shade, can also be dried with normal temperature, drying temperature is 50 DEG C~150 DEG C.
Metallic element in the metal salt is Pd, Pt, Ru, Ag, Ni, Cu, Au, Li, Rh, Ir, Ce, Sc, Fe, Mo, Co,
One or more in W, the metal salt is the sulfate of above-mentioned metallic element, nitrate, acetate, carbonate, chlorate,
One or more in Bromide, preferably copper nitrate or iron chloride.
The molar ratio of metal ion and 1,3,5- benzenetricarboxylic acids is in the metal salt（0.5~5）:1, be preferably（0.9
~3）:1, described 1, the part by weight of 3,5- benzenetricarboxylic acids and the second solvent is 1:（0.5~100）, preferably 1:（1~40）.
Second solvent is the mixed solution containing alcohols solvent and nitrogen-containing compound solvent.The alcohols solvent is with containing
The part by weight of nitrogen compound solvent is（0.1~10）:1, be preferably（0.5~5）:1.The alcohols solvent be methanol, ethanol,
It is propyl alcohol, isopropanol, butanol, isobutanol, amylalcohol, 3- methyl -2- butanol, hexanol, 2- ethyl butanols, 2- methyl anyl alcohols, enanthol, pungent
Alcohol, lauryl alcohol, tetradecyl alchohol, pentadecanol, hexadecanol, heptadecanol, octadecyl alcolol, cyclopentanol, cyclohexanol, benzyl carbinol, ethylene glycol, the third two
One or more in alcohol, butanediol, pentaerythrite, preferably methanol, ethanol, propyl alcohol, butanol, isobutanol, hexanol, 2- ethyls
One or more in butanol, enanthol, cyclopentanol, butanediol, pentaerythrite, more preferably methanol；
The nitrogen-containing compound solvent be nitrobenzene, acetonitrile, propionitrile, succinonitrile, methylamine, dimethylamine, ethamine, triethylamine, butylamine,
Isobutyl amine, sec-butylamine, tert-butylamine, tri-n-butylamine, aniline, cyclohexylamine, pyrroles, pyridine, quinoline, formamide, N-METHYLFORMAMIDE, N,
Dinethylformamide, N, in N- diethylformamides, DMAC N,N' dimethyl acetamide, N- methylacetamides, N- methyl propanamides
One or more, preferably nitrobenzene, ethamine, tri-n-butylamine, pyrroles, pyridine, quinoline, DMF, N, N- bis-
One or more in ethyl-formamide, N- methyl propanamides, more preferably DMA.
In step（2）In, 80 DEG C~300 DEG C, time 5h~40h of the temperature of the crystallization, drying temperature 100 DEG C~300
DEG C, drying time 5h~24h.Separation can select filtering, centrifuge the methods of, solvent used in washing can be water,
One or more in ethanol, methanol, chloroform, preferably water, can be to carry out during washing under heating condition, and wash temperature is 30 DEG C
~50 DEG C.
Present invention also offers a kind of metal-organic framework materials prepared such as above-mentioned method.
The property of metal-organic framework materials of the present invention is as follows：Specific surface area is 500m2/ g~3000m2/ g, it is excellent
Elect 1000m as2/ g~2500m2/ g, total pore volume 0.3cm3/ g~0.9cm3/ g, preferably 0.4cm3/ g~0.7cm3/g。
The relative crystallinity of metal-organic framework materials of the present invention is 95%~100%.
The average grain diameter of metal-organic framework materials of the present invention is 0.1 μm~10 μm, preferably 0.5 μm~6 μm.
Present invention also offers above-mentioned metal-organic framework materials in middle gas absorption, gas absorption storage, gas absorption
Application in separation.
Described metal-organic framework materials are inhaled in carbon dioxide, hydrogen, methane, carbon monoxide, nitrogen, ethane, propane
Attached storage, and carbon dioxide/methane, carbon dioxide/carbon monoxide, titanium dioxide carbon/nitrogen gas, carbon dioxide/oxygen, hydrogen/
Carbon dioxide, hydrogen/nitrogen, methane/nitrogen, ethane/ethylene, propane/propylene gaseous mixture be selectively adsorbing and separating in application.
Compared with prior art, the inventive method has following outstanding advantages：
（1）The preparation method of the metal-organic framework materials of the present invention, using the cheap benzenetricarboxylic acid of technical grade 1,3,5-
As raw material, and a certain amount of surfactant is with the addition of in 1,3,5- benzenetricarboxylic acid recrystallizes dedoping step, not only enter one
Step improves the purity of 1,3,5- benzenetricarboxylic acids, controls the further growth of crystal, and a small amount of surfactant can also enter
Enter the crystals of recrystallization, match somebody with somebody so as to enhance 1,3,5- benzenetricarboxylic acids in metal organic framework building-up process as organic
Body synthesizes the reactivity of metal-organic framework materials, avoids the reunion between metal-organic framework materials crystal, raising has
The utilization rate and product yield of machine part, specific surface area is higher and the high metal-organic framework materials of pore volume for synthesis, greatly carries
High industrial application value.
（2）The preparation method of the metal-organic framework materials of the present invention, with the mixed of alcohols solvent and nitrogen-containing compound solvent
Solvent of the solution as synthesis metal-organic framework materials is closed, provide not only the growth of metal-organic framework materials crystalline framework
Environment, also acted on template, further improve product yield, easily controllable pore passage structure and size, metal organic framework
Stability of material is good, service life length, improves the applicability of metal-organic framework materials.
（3）The metal-organic framework materials of the present invention, there is very high crystallinity, specific surface area, total pore volume, Ke Yiyong
Application in gas absorption, gas absorption storage, gas absorption separation, especially in carbon dioxide, hydrogen, methane, an oxygen
Change the storage of the gas absorptions such as carbon, nitrogen, ethane, propane, and carbon dioxide/methane, carbon dioxide/carbon monoxide, titanium dioxide
Carbon/nitrogen gas, carbon dioxide/oxygen, hydrogen/carbon dioxide, hydrogen/nitrogen, methane/nitrogen, ethane/ethylene, propane/propylene etc.
Gaseous mixture be selectively adsorbing and separating in application.
Brief description of the drawings
Fig. 1 is the XRD for the Cu Base Metal organic framework materials that embodiment 1,2,3,6,7 synthesizes with comparative example 1,2,3,4
Spectrum；
Fig. 2 is the XRD spectrum for the Fe Base Metal organic framework materials that embodiment 4 synthesizes；
Fig. 3 is the XRD spectrum for the Cr Base Metal organic framework materials that embodiment 5 synthesizes；
Fig. 4 is the ESEM of metal-organic framework materials of the sample A of embodiment 1 after 200 DEG C of roastings（SEM）Figure；
The ESEM of metal-organic framework materials of the sample B of Fig. 5 embodiments 2 after 200 DEG C of roastings（SEM）Figure；
Fig. 6 is the ESEM of metal-organic framework materials of the sample C of embodiment 3 after 200 DEG C of roastings（SEM）Figure；
Fig. 7 is the ESEM of metal-organic framework materials of the sample F of embodiment 6 after 200 DEG C of roastings（SEM）Figure；
Fig. 8 is the ESEM of metal-organic framework materials of the sample H of comparative example 1 after 200 DEG C of roastings（SEM）Figure；
Fig. 9 is the ESEM of metal-organic framework materials of the sample I of comparative example 2 after 200 DEG C of roastings（SEM）Figure；
Figure 10 is the sample C adsorbed methane curves of embodiment 3.
Embodiment
Further illustrate the preparation process of metal-organic framework materials of the present invention below by embodiment, but it is not considered that
Present invention is limited only by following embodiment, wherein wt% is mass fraction.
Embodiment 1
（1）Purify 1,3,5- benzenetricarboxylic acids
By thick the 1 of 100.12g, 3,5- benzenetricarboxylic acids, 2.84g 1-METHYLPYRROLIDONE, it is added in 260mL ethanol, with 0.5
DEG C/min heating rates are warming up to 30 DEG C, it is completely dissolved under conditions of stirring and keeps 30min, then filters out micro 1,
3,5- benzenetricarboxylic acids and impurity, filtrate is cooled to 10 DEG C with 0.5 DEG C/min rate of temperature fall and keeps 30min, thick 1,3,5- benzene
Tricarboxylic acid progressively separates out crystallization, then through separation of solid and liquid, dry after purified after 1,3,5- benzenetricarboxylic acids.
（2）Prepare metal-organic framework materials
By the 1,3,5- benzenetricarboxylic acids, 8.82g copper nitrates, the solvents of 12mL second of 10.12g purifications（Methanol：N, N- dimethylacetamide
Amine=0.5:1）Well mixed to be put into reactor, 120 DEG C of crystallization 12h, crystallization is washed products therefrom after terminating, filtering
Product is placed at 200 DEG C afterwards and dries 12h, obtains Cu Base Metal organic framework material A, particle size range is 4 μm~5 μm.
Embodiment 2
（1）Purify 1,3,5- benzenetricarboxylic acids
By thick the 1 of 100.45g, 3,5- benzenetricarboxylic acids, 10.12g 1-METHYLPYRROLIDONE, it is added in 640mL ethanol, with 10
DEG C/min heating rates are warming up to 100 DEG C, it is completely dissolved under conditions of stirring and keeps 120min, is then filtered out micro
1,3,5- benzenetricarboxylic acid and impurity, filtrate is cooled to 25 DEG C with 10 DEG C/min rate of temperature fall and keeps 120min, thick 1,3,5-
Benzenetricarboxylic acid progressively separates out crystallization, then through separation of solid and liquid, dry after purified after 1,3,5- benzenetricarboxylic acids.
（2）Prepare metal-organic framework materials
By the 1,3,5- benzenetricarboxylic acids, 26.45g copper nitrates, the solvents of 500mL second of 10g purifications（Methanol：N, N- dimethylacetamide
Amine=5:1）Well mixed to be put into reactor, 120 DEG C of crystallization 12h, crystallization is washed products therefrom after terminating, after filtering
Product is placed at 200 DEG C and dries 12h, obtains Cu Base Metal organic framework material B, particle size range is 4 μm~6 μm.
Embodiment 3
（1）Purify 1,3,5- benzenetricarboxylic acids
By thick the 1 of 100.12g, 3,5- benzenetricarboxylic acids, 4.14g 1-METHYLPYRROLIDONE, it is added in 400mL ethanol, with 5
DEG C/min heating rates are warming up to 80 DEG C, it is completely dissolved under conditions of stirring and keeps 60min, then filters out micro 1,
3,5- benzenetricarboxylic acids and impurity, filtrate is cooled to 15 DEG C with 5 DEG C/min rate of temperature fall and keeps 60min, thick 1,3,5- benzene three
Formic acid progressively separates out crystallization, then through separation of solid and liquid, dry after purified after 1,3,5- benzenetricarboxylic acids.
（2）Prepare metal-organic framework materials
By the 1,3,5- benzenetricarboxylic acids, 23.58g copper nitrates, the solvents of 240mL second of 10.12g purifications（Methanol：N, N- dimethyl second
Acid amides=1:1）Well mixed to be put into reactor, 120 DEG C of crystallization 12h, crystallization is washed products therefrom after terminating, filtering
Product is placed at 200 DEG C afterwards and dries 12h, obtains Cu Base Metal organic framework material C, particle size range is 0.5 μm~1.2 μm.
Embodiment 4
（1）Purify 1,3,5- benzenetricarboxylic acids
By thick the 1 of 100.12g, 3,5- benzenetricarboxylic acids, 4.14g 1-METHYLPYRROLIDONE, it is added in 400mL ethanol, with 5
DEG C/min heating rates are warming up to 80 DEG C, it is completely dissolved under conditions of stirring and keeps 60min, then filters out micro 1,
3,5- benzenetricarboxylic acids and impurity, filtrate is cooled to 15 DEG C with 5 DEG C/min rate of temperature fall and keeps 60min, thick 1,3,5- benzene three
Formic acid progressively separates out crystallization, then through separation of solid and liquid, dry after purified after 1,3,5- benzenetricarboxylic acids.
（2）Prepare metal-organic framework materials
By the 1,3,5- benzenetricarboxylic acids, 12.93g iron chloride, the solvents of 300mL second of 10g purifications（Methanol：N, N- dimethylacetamide
Amine=1:1）Well mixed to be put into reactor, 180 DEG C of crystallization 8h, crystallization is washed products therefrom after terminating, will after filtering
Product, which is placed at 200 DEG C, dries 5h, obtains Fe Base Metal organic framework material D, and particle size range is 1.2 μm~2.6 μm.
Embodiment 5
（1）Purify 1,3,5- benzenetricarboxylic acids
By thick the 1 of 100.12g, 3,5- benzenetricarboxylic acids, 4.14g 1-METHYLPYRROLIDONE, it is added in 400mL ethanol, with 5
DEG C/min heating rates are warming up to 80 DEG C, it is completely dissolved under conditions of stirring and keeps 60min, then filters out micro 1,
3,5- benzenetricarboxylic acids and impurity, filtrate is cooled to 15 DEG C with 5 DEG C/min rate of temperature fall and keeps 60min, thick 1,3,5- benzene three
Formic acid progressively separates out crystallization, then through separation of solid and liquid, dry after purified after 1,3,5- benzenetricarboxylic acids.
（2）Prepare metal-organic framework materials
By the 1,3,5- benzenetricarboxylic acids, 15.19g chromic nitrates, the solvents of 400mL second of 10g purifications（Methanol：N, N- dimethylacetamide
Amine=1:1）Well mixed to be put into reactor, 220 DEG C of crystallization 36h, crystallization is washed products therefrom after terminating, after filtering
Product is placed at 200 DEG C and dries 5h, obtains Cr Base Metal organic framework material E, particle size range is 0.1 μm~0.6 μm.
Embodiment 6
For the preparation method of metal-organic framework materials with embodiment 3, difference is that surfactant is addition dodecyl
Benzene sulfonic acid sodium salt, other reaction condition and material compositions are constant, obtain Cu Base Metal organic framework materials F.
Embodiment 7
The preparation method of metal-organic framework materials is with embodiment 3, and difference is that the second solvent is propyl alcohol and ethamine, and it compares
Example is 1:1, other reaction condition and material compositions are constant, obtain Cu Base Metal organic framework materials G.
Comparative example 1
With embodiment 3, difference is in step the preparation method of metal-organic framework materials（1）Purify 1,3,5- benzene front threes
1-METHYLPYRROLIDONE is not added in the process of acid, and step（2）Mixed in 1,3,5- benzenetricarboxylic acids, copper nitrate and the second solvent
Shi Tianjia 4.14g 1-METHYLPYRROLIDONE, obtains Cu Base Metal organic framework material H, and particle size range is 0.1 μm~0.3 μm.
Comparative example 2
With embodiment 3, difference is without using surfactant the preparation method of metal-organic framework materials, obtains Cu bases
Metal-organic framework materials I, particle size range are 0.1 μm~0.2 μm.
Comparative example 3
For the preparation method of metal-organic framework materials with embodiment 3, difference is that the second solvent is methanol, obtains Cu funds
Belong to organic framework material J.
Comparative example 4
The preparation method of metal-organic framework materials is with embodiment 3, and difference is that the second solvent is N, N- dimethylacetamides
Amine, obtain Cu Base Metal organic framework materials K.
Table 1
| Industrial 1,3,5- benzenetricarboxylic acids purity/wt% | 1,3,5- benzenetricarboxylic acids purity/wt% after purification | Utilization rate/wt% of 1,3,5- benzenetricarboxylic acids | |
| Embodiment 1 | 65 | 99.5 | 92 |
| Embodiment 2 | 65 | 99.5 | 91 |
| Embodiment 3 | 65 | 99.5 | 98 |
| Embodiment 4 | 65 | 99.5 | 96 |
| Embodiment 5 | 65 | 99.5 | 95 |
| Embodiment 6 | 65 | 98.4 | 93 |
| Embodiment 7 | 65 | 99.5 | 92 |
| Comparative example 1 | 65 | 97.1 | 88 |
| Comparative example 2 | 65 | 91.5 | 81 |
| Comparative example 3 | 65 | 99.5 | 85 |
| Comparative example 4 | 65 | 99.5 | 84 |
As can be seen from Table 1, thick 1, the purity of 1,3,5- benzenetricarboxylic acids is increased substantially after 3,5- benzenetricarboxylic acids are purified, it is reachable
To more than 99.5%, the surfactant of addition further increases the ligand 1 in metal-organic framework materials building-up process, and 3,
The utilization rate of 5- benzenetricarboxylic acids, up to 98wt%.
Test case 1
The physico-chemical property of embodiment 1-4,6-7 and comparative example 1-4 metal-organic framework materials is determined, concrete outcome is shown in Table 2.Its
In, BET specific surface area, pore volume are measured by low temperature liquid nitrogen absorption method.For the measure of relative crystallinity, embodiment 1-3,6-7 and
With comparative example 1-4 sample to buy the metal-organic framework materials Cu of BASF Corp. of Germany3(BTC)2On the basis of（Basolite
® C300）, set its crystallinity and be calculated as 100%, crystallinity is determined by XRD methods.The sample of embodiment 4 is to buy moral
The metal-organic framework materials Fe-BTC of BASF AG of state（Basolite® F300）On the basis of, its crystallinity is set as 100%
It is calculated, crystallinity is determined by XRD methods.
The physicochemical property of 2 each metal-organic framework materials of table
| Sample | BET specific surface area/m2·g-1 | Total pore volume/cm3·g-1 | Relative crystallinity/% | Heat endurance（250 DEG C of roasting 10h） |
| A | 1293 | 0.54 | 93 | Structural integrity |
| B | 1366 | 0.55 | 95 | Structural integrity |
| C | 1480 | 0.62 | 105 | Structural integrity |
| D | 2600 | 0.74 | 98 | Structural integrity |
| E | 1980 | 0.71 | - | Structural integrity |
| F | 1341 | 0.57 | 92 | Structural integrity |
| G | 1284 | 0.51 | 93 | Structural integrity |
| H | 927 | 0.45 | 90 | Structure collapse |
| I | 862 | 0.44 | 78 | Structure collapse |
| J | 956 | 0.45 | 82 | Structure collapse |
| K | 929 | 0.43 | 80 | Structure collapse |
As can be seen from Table 2, the metal-organic framework materials that prepared by 1-7 of the embodiment of the present invention have very high specific surface area,
But also there is higher crystallinity and preferable heat endurance, the metal-organic framework materials prepared far above comparative example 1-4.
Test case 2
The methane adsorption of measure embodiment 1-3,6,7 and comparative example 1-4 metal-organic framework materials measures test result and is shown in Table 3.
Methane adsorption amount：Methane High Pressure Absorption uses Micromeritics HPVA-100 type adsorption instruments.Before sample test,
12h is first vacuumized at 200 DEG C on adsorption instrument, evacuated pressure is less than 10 μm of Hg, is then instructed in programmed pressure processing module
Under, reach 40bar and 298K, and obtain corresponding quality storage methane content.
The methane adsorption amount of 3 each metal-organic framework materials of table
| Sample | Methane adsorption amount/cm3/g |
| A | 185 |
| B | 189 |
| C | 204 |
| F | 175 |
| G | 181 |
| H | 140 |
| I | 106 |
| J | 127 |
| K | 135 |
The adsorbed methane effect data further explanation that table 2 provides, metal organic framework prepared by 1-3 of the embodiment of the present invention, 6,7
Material has higher methane adsorption amount.
Fig. 1 is the XRD for the Cu Base Metal organic framework materials that embodiment 1,2,3,6,7 synthesizes with comparative example 1,2,3,4
Spectrum；Pass through characteristic peak, present invention synthesis metal-organic framework materials Cu3(BTC)2.Fig. 2 is the Fe funds that embodiment 4 synthesizes
Belong to the XRD spectrum of organic framework material, pass through characteristic peak, present invention synthesis metal-organic framework materials Fe-BTC；Fig. 3 is
The XRD spectrum for the Cr Base Metal organic framework materials that embodiment 5 synthesizes, by characteristic peak, present invention synthesis metal is organic
Framework material Cr-BTC.
Fig. 4 is the ESEM of metal-organic framework materials of the sample A of embodiment 1 after 200 DEG C of roastings（SEM）Figure；
The ESEM of metal-organic framework materials of the sample B of Fig. 5 embodiments 2 after 200 DEG C of roastings（SEM）Figure；Fig. 6 is embodiment
The ESEM of metal-organic framework materials of the 3 sample C after 200 DEG C of roastings（SEM）Figure；Fig. 7 is the sample F of embodiment 6
The ESEM of metal-organic framework materials after 200 DEG C of roastings（SEM）Figure；Fig. 8 is the sample H of comparative example 1 through 200 DEG C of roastings
The ESEM of metal-organic framework materials after burning（SEM）Figure；Fig. 9 is gold of the sample I of comparative example 2 after 200 DEG C of roastings
Belong to the ESEM of organic framework material（SEM）Figure；
By contrast, it can be found that after the metal-organic framework materials of embodiment 1,3 and 6 are calcined 10h at 200 DEG C, still protect
Complete pattern and skeleton structure have been held, and after the metal-organic framework materials of comparative example 1 and 2 are calcined 10h at 200 DEG C, bone
Frame caves in completely, can not differentiate clear pattern.
Claims (19)
1. a kind of preparation method of metal-organic framework materials, it is characterised in that comprise the following steps：
（1）Thick 1,3,5- benzenetricarboxylic acid is added in the first solvent and recrystallized, 1 after being purified, 3,5- benzene front threes
Acid, the recrystallization includes rising temperature for dissolving, cool the step of separating out, wherein before thick 1,3,5- benzenetricarboxylic acid rising temperature for dissolving, rising
Surfactant is introduced in warm course of dissolution and/or after rising temperature for dissolving and before cooling separates out；
（2）By 1 after purification, 3,5- benzenetricarboxylic acids, metal salt and the second solvent are well mixed, then crystallization, separation, washing and
Dry, obtain described metal-organic framework materials.
2. in accordance with the method for claim 1, it is characterised in that：The thick 1,3,5- benzenetricarboxylic acids, surfactant and the
The part by weight of one solvent is 1:（0.01~0.5）:（1~50）, preferably 1:（0.02~0.1）:（2~5）.
3. in accordance with the method for claim 1, it is characterised in that：The surfactant be 1-METHYLPYRROLIDONE, tween-
20th, in Tween-40, Tween-60, Tween-80, Arlacel-20, Arlacel-40, Arlacel-60, Arlacel-80, neopelex
One or more, preferably 1-METHYLPYRROLIDONE.
4. in accordance with the method for claim 1, it is characterised in that：First solvent is low-carbon alcohols, preferably methanol, second
One or more in alcohol, propyl alcohol, butanol, ethylene glycol, more preferably ethanol.
5. in accordance with the method for claim 1, it is characterised in that：The purity of the thick 1,3,5- benzenetricarboxylic acids for 50wt%~
70wt%。
6. in accordance with the method for claim 1, it is characterised in that：The purity of 1,3,5- benzenetricarboxylic acids after the purification is
80.00wt%~99.99wt%, preferably 90.0wt%~99.9wt%.
7. in accordance with the method for claim 1, it is characterised in that：In step（1）In, the specific steps of the rising temperature for dissolving
For：30 DEG C~100 DEG C are increased to 0.5 DEG C/min~10 DEG C/min heating rate, and keeps 30min~2h.
8. in accordance with the method for claim 1, it is characterised in that：In step（1）In, the specific steps of the cooling precipitation
For：10 DEG C~25 DEG C are cooled to 0.5 DEG C/min~10 DEG C/min rate of temperature fall, and keeps 30min~2h.
9. in accordance with the method for claim 1, it is characterised in that：The recrystallization also includes：After cooling separates out, divided
From, washing and dry step.
10. in accordance with the method for claim 1, it is characterised in that：Metallic element in the metal salt is Pd, Pt, Ru,
One or more in Ag, Ni, Cu, Au, Li, Rh, Ir, Ce, Sc, Fe, Mo, Co, W, the metal salt are above-mentioned metallic element
Sulfate, nitrate, acetate, carbonate, chlorate, the one or more in Bromide, preferably copper nitrate or chlorination
Iron.
11. in accordance with the method for claim 1, it is characterised in that：Metal ion and 1,3,5- benzene front threes in the metal salt
Acid molar ratio be（0.5~5）:1, be preferably（0.9~3）:1, described 1, the weight of 3,5- benzenetricarboxylic acids and the second solvent
Ratio is 1:（0.5~100）, preferably 1:（1~40）.
12. in accordance with the method for claim 1, it is characterised in that：Second solvent is to contain alcohols solvent and nitrogen
The mixed solution of compound solvent.
13. in accordance with the method for claim 12, it is characterised in that：The weight of the alcohols solvent and nitrogen-containing compound solvent
Ratio is（0.1~10）:1, be preferably（0.5~5）:1.
14. according to the method described in claim 12 or 13, it is characterised in that：The alcohols solvent be methanol, ethanol, propyl alcohol,
Isopropanol, butanol, isobutanol, amylalcohol, 3- methyl -2- butanol, hexanol, 2- ethyl butanols, 2- methyl anyl alcohols, enanthol, octanol, ten
Glycol, tetradecyl alchohol, pentadecanol, hexadecanol, heptadecanol, octadecyl alcolol, cyclopentanol, cyclohexanol, benzyl carbinol, ethylene glycol, propane diols, fourth
One or more in glycol, pentaerythrite, preferably methanol, ethanol, propyl alcohol, butanol, isobutanol, hexanol, 2- ethyl butanols,
One or more in enanthol, cyclopentanol, butanediol, pentaerythrite, more preferably methanol；
The nitrogen-containing compound solvent be nitrobenzene, acetonitrile, propionitrile, succinonitrile, methylamine, dimethylamine, ethamine, triethylamine, butylamine,
Isobutyl amine, sec-butylamine, tert-butylamine, tri-n-butylamine, aniline, cyclohexylamine, pyrroles, pyridine, quinoline, formamide, N-METHYLFORMAMIDE, N,
Dinethylformamide, N, in N- diethylformamides, DMAC N,N' dimethyl acetamide, N- methylacetamides, N- methyl propanamides
One or more, preferably nitrobenzene, ethamine, tri-n-butylamine, pyrroles, pyridine, quinoline, DMF, N, N- bis-
One or more in ethyl-formamide, N- methyl propanamides, more preferably DMA.
15. in accordance with the method for claim 1, it is characterised in that：In step（2）In, the temperature 80 DEG C~300 of the crystallization
DEG C, time 5h~40h, 100 DEG C~300 DEG C of drying temperature, drying time 5h~24h.
A kind of 16. metal-organic framework materials prepared by method as described in claim 1-15 is any.
17. according to the metal-organic framework materials described in claim 16, it is characterised in that：The metal-organic framework materials
Property is as follows：Specific surface area is 500m2/ g~3000m2/ g, preferably 1000m2/ g~2500m2/ g, total pore volume 0.3cm3/g
~0.9cm3/ g, preferably 0.4cm3/ g~0.7cm3/g。
18. according to the metal-organic framework materials described in claim 16, it is characterised in that：The metal-organic framework materials
Average grain diameter is 0.1 μm~10 μm, preferably 0.5 μm~6 μm.
19. according to the metal-organic framework materials described in claim 16, it is characterised in that：The metal-organic framework materials
Relative crystallinity is 95%~100%.
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