CN107774329B - Metal organic framework material and preparation method thereof - Google Patents
Metal organic framework material and preparation method thereof Download PDFInfo
- Publication number
- CN107774329B CN107774329B CN201610736797.0A CN201610736797A CN107774329B CN 107774329 B CN107774329 B CN 107774329B CN 201610736797 A CN201610736797 A CN 201610736797A CN 107774329 B CN107774329 B CN 107774329B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal
- solvent
- framework material
- tricarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 105
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 abstract description 158
- 239000002904 solvent Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000004090 dissolution Methods 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 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 42
- 238000000926 separation method Methods 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- -1 nitrogen-containing compound Chemical class 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-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
- 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 claims description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-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
- 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
- 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-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
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-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
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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 compound 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 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
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 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
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 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
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000013084 copper-based metal-organic framework Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000013148 Cu-BTC MOF 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
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000013147 Cu3(BTC)2 Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013087 chromium-based metal-organic framework Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000013082 iron-based metal-organic framework Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002994 raw material 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
- 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
- 239000005977 Ethylene Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229940026110 carbon dioxide / nitrogen Drugs 0.000 description 2
- 229940026085 carbon dioxide / oxygen Drugs 0.000 description 2
- 229940105305 carbon monoxide Drugs 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 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
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000013151 Basolite® C 300 Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 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 description 1
- 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 description 1
- 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 description 1
- 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 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013289 nano-metal-organic framework Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01J20/28057—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
-
- 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
- B01J20/28057—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
-
- 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
-
- 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
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a metal organic framework material and a preparation method thereof. The method comprises the following steps: (1) adding crude 1,3, 5-benzene tricarboxylic acid into a first solvent for recrystallization to obtain purified 1,3, 5-benzene tricarboxylic acid, wherein the recrystallization comprises the steps of heating up for dissolution and cooling down for precipitation, and a surfactant is introduced before the crude 1,3, 5-benzene tricarboxylic acid is heated up for dissolution, in the heating up for dissolution and/or after the heating up for dissolution and before the cooling down for precipitation; (2) and uniformly mixing the purified 1,3, 5-benzene tricarboxylic acid, the metal salt and the second solvent, and then crystallizing, separating, washing and drying to obtain the metal organic framework material. According to the method, the surfactant is added in the recrystallization process of the 1,3, 5-benzenetricarboxylic acid, so that the purity of the 1,3, 5-benzenetricarboxylic acid is improved, and a small amount of the surfactant can enter the interior of a recrystallized crystal, so that the agglomeration of crystals in the synthesis process of the metal organic framework material is avoided, and the specific surface area and the pore volume of the metal organic framework material are improved.
Description
Technical Field
The invention relates to a metal organic framework material and a preparation method thereof.
Background
The Metal-Organic Frameworks (MOFs for short) are zeolite-like Frameworks which are formed by self-assembling polydentate Organic ligands containing oxygen, nitrogen and the like and transition Metal ions and have special pore channel structures. The adsorbent and the separating agent have the advantages of high porosity, large specific surface area, small density, adjustable pore size structure, composition and functional design and the like, and provide an opportunity for developing an energy gas adsorbent and a separating agent with high storage capacity and high shape-selective separation effect.
Cu3(BTC)2Also called HKUST-1 type metal organic framework material, the coordination polymer is formed by self-assembling binuclear copper clusters and trimesic acid. It is crystallized in a cubic system and belongs to a space group Fm-3 m. When removing water bound to copper ions from the framework, Cu3(BTC)2Will become a three-dimensional porous structure with an unsaturated metal coordination structure having a primary channel dimension of 9 Å, a slightly smaller tetrahedral edge pocket dimension of 5 Å, and connected to the primary channel by a triangular aperture window of 3.5 Å3(BTC)2Has two typical holes, so that the material is not only good for gas molecule adsorption, but also good for mixed gas separation.
At present, Cu is mainly prepared by a hydrothermal synthesis method3(BTC)2A material. For example, CN 102863463A discloses a method for preparing Cu-BTC and nano Cu-BTC, first Cu (ClO)4)2And an ethanol solution of 1,3, 5-benzenetricarboxylic acid to prepare synthetic Cu (C)9H406)(H2O), and then soaking in an organic solvent or steam environment to obtain the Cu-BTC.
CN102336774A discloses a method for rapidly synthesizing a nano-scale metal organic framework nano-material based on trimesic acid at room temperature. And (3) mixing the metal acetate aqueous solution and the trimesic acid solution at room temperature, and then reacting to obtain the metal organic framework nano-particles. The method belongs to a dynamic synthesis process, is carried out at room temperature, and has the advantages of rapidness, simplicity, convenience, energy conservation, high yield and the like.
CN103920158A discloses a method for synthesizing a nano-sized metal-organic framework, which comprises using a surfactant as a template, using a rigid ligand containing an atom capable of providing a lone electron pair, such as N or O, as an organic ligand, and using ions of one or more metal elements selected from alkaline earth metal elements, lanthanide metal elements, transition metal elements, and amphoteric elements as metal ions, and synthesizing the nano-sized metal-organic framework by a hydrothermal method, a microwave method, or an ultrasonic method.
However, in the preparation process of the metal organic framework material, high-purity 1,3, 5-benzenetricarboxylic acid is adopted as a raw material, so that the production cost is high, and the industrial popularization is not facilitated. The industrial ligand with lower purity is used for synthesizing the metal organic framework material, the crystallinity is poorer, the specific surface area is smaller, and the feasibility of the practical application of the metal organic framework material is greatly reduced.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a metal organic framework material and a preparation method thereof. The method takes the industrial grade 1,3, 5-benzene tricarboxylic acid with lower purity as a raw material to synthesize the metal organic framework material, and the metal organic framework material not only has very high crystallinity, specific surface area, total pore volume and thermal stability, but also has very high yield.
The invention provides a preparation method of a metal organic framework material, which comprises the following steps:
(1) adding crude 1,3, 5-benzene tricarboxylic acid into a first solvent for recrystallization to obtain purified 1,3, 5-benzene tricarboxylic acid, wherein the recrystallization comprises the steps of heating up for dissolution and cooling down for precipitation, and a surfactant is introduced before the crude 1,3, 5-benzene tricarboxylic acid is heated up for dissolution, in the heating up for dissolution and/or after the heating up for dissolution and before the cooling down for precipitation;
(2) and uniformly mixing the purified 1,3, 5-benzene tricarboxylic acid, the metal salt and the second solvent, and then crystallizing, separating, washing and drying to obtain the metal organic framework material.
The surfactant is one or more of N-methylpyrrolidone, Tween-20, Tween-40, Tween-60, Tween-80, span-20, span-40, span-60, span-80 and sodium dodecyl benzene sulfonate, and preferably N-methylpyrrolidone.
The first solvent is a low-carbon alcohol, preferably one or more of methanol, ethanol, propanol, butanol and ethylene glycol, and more preferably ethanol.
The crude 1,3, 5-benzene tricarboxylic acid can be 1,3, 5-benzene tricarboxylic acid with relatively low purity, such as industrial grade 1,3, 5-benzene tricarboxylic acid, and the purity of the crude 1,3, 5-benzene tricarboxylic acid can be 50wt% to 70 wt%.
After purification by the method of the present invention, the purity of the purified 1,3, 5-benzenetricarboxylic acid can be 80.00wt% to 99.99wt%, preferably 90.0wt% to 99.9 wt%.
The weight ratio of the crude 1,3, 5-benzene tricarboxylic acid, the surfactant and the first solvent is 1 (0.01-0.5) to (1-50), and preferably 1 (0.02-0.1) to (2-5).
In the step (1), the heating dissolution may specifically be: raising the temperature to 30-100 ℃ at the heating rate of 0.5-10 ℃/min and keeping the temperature for 30-2 h. In the step (1), the specific steps of cooling and precipitating may be: cooling to 10-25 ℃ at the cooling rate of 0.5-10 ℃/min and keeping for 30 min-2 h.
In the step (1), the recrystallization may further include the steps of separating, washing and drying after the temperature reduction and precipitation. The separation can be selected from conventional separation methods such as filtration and centrifugal separation, the drying condition has no special requirements, the drying can be realized, the drying can be carried out at normal temperature in the shade, and the drying can also be carried out at the drying temperature of 50-150 ℃.
The metal element in the metal salt is one or more of Pd, Pt, Ru, Ag, Ni, Cu, Au, Li, Rh, Ir, Ce, Sc, Fe, Mo, Co and W, the metal salt is one or more of sulfate, nitrate, acetate, carbonate, chloride and bromide of the metal element, and preferably copper nitrate or ferric chloride.
The molar ratio of the metal ions to the 1,3, 5-benzene tricarboxylic acid in the metal salt is (0.5-5): 1, preferably (0.9-3): 1, and the weight ratio of the 1,3, 5-benzene tricarboxylic acid to the second solvent is 1 (0.5-100), preferably 1 (1-40).
The second solvent is a mixed solution containing an alcohol solvent and a nitrogen-containing compound solvent. The weight ratio of the alcohol solvent to the nitrogen-containing compound solvent is (0.1-10): 1, preferably (0.5-5): 1. The alcohol solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, 3-methyl-2-butanol, hexanol, 2-ethyl butanol, 2-methyl pentanol, heptanol, octanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, cyclopentanol, cyclohexanol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol and pentaerythritol, preferably one or more of methanol, ethanol, propanol, butanol, isobutanol, hexanol, 2-ethyl butanol, heptanol, cyclopentanol, butanediol and pentaerythritol, and more preferably methanol;
the nitrogen-containing compound solvent is one or more of nitrobenzene, acetonitrile, propionitrile, succinonitrile, methylamine, dimethylamine, ethylamine, triethylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, tributylamine, aniline, cyclohexylamine, pyrrole, pyridine, quinoline, formamide, N-methylformamide, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-methylacetamide and N-methylpropionamide, preferably one or more of nitrobenzene, ethylamine, tributylamine, pyrrole, pyridine, quinoline, N-dimethylformamide, N-diethylformamide and N-methylpropionamide, and more preferably N, N-dimethylacetamide.
In the step (2), the crystallization temperature is 80-300 ℃, the crystallization time is 5-40 h, the drying temperature is 100-300 ℃, and the drying time is 5-24 h. The separation can be selected from filtration, centrifugal separation, etc., and the washing solvent can be one or more of water, ethanol, methanol, and chloroform, preferably water, and the washing can be carried out under heating at 30-50 deg.C.
The invention also provides the metal organic framework material prepared by the method.
The properties of the metal organic framework material are as follows: the specific surface area is 500m2/g～3000m2A/g, preferably of 1000m2/g～2500m2(g) total pore volume of 0.3cm3/g～0.9cm3Per g, preferably 0.4cm3/g～0.7cm3/g。
The relative crystallinity of the metal organic framework material is 95 to 100 percent.
The metal organic framework material has an average particle size of 0.1 to 10 μm, preferably 0.5 to 6 μm.
The invention also provides application of the metal organic framework material in gas adsorption, gas adsorption storage and gas adsorption separation.
The metal organic framework material is applied to adsorption storage of carbon dioxide, hydrogen, methane, carbon monoxide, nitrogen, ethane and propane, and selective adsorption separation of carbon dioxide/methane, carbon dioxide/carbon monoxide, carbon dioxide/nitrogen, carbon dioxide/oxygen, hydrogen/carbon dioxide, hydrogen/nitrogen, methane/nitrogen, ethane/ethylene and propane/propylene mixed gas.
Compared with the prior art, the method has the following outstanding advantages:
(1) the preparation method of the metal organic framework material adopts the cheap industrial grade 1,3, 5-benzene tricarboxylic acid as the raw material, and a certain amount of surfactant is added in the recrystallization and impurity removal process of the 1,3, 5-benzene tricarboxylic acid, so that the purity of the 1,3, 5-benzene tricarboxylic acid is further improved, the further growth of the crystal is controlled, a small amount of surfactant can enter the interior of the recrystallized crystal, therefore, the reaction activity of the 1,3, 5-benzene tricarboxylic acid used as the organic ligand for synthesizing the metal organic framework material is enhanced in the synthesis process of the metal organic framework, the agglomeration among metal organic framework material crystals is avoided, the utilization rate and the product yield of the organic ligand are improved, the metal organic framework material with higher specific surface area and high pore volume is synthesized, and the industrial application value is greatly improved.
(2) The preparation method of the metal organic framework material takes the mixed solution of the alcohol solvent and the nitrogen-containing compound solvent as the solvent for synthesizing the metal organic framework material, not only provides the environment for the growth of the crystal framework of the metal organic framework material, but also has the function of the template agent, further improves the product yield, is easy to control the pore structure and size, has good stability and long service life of the metal organic framework material, and improves the applicability of the metal organic framework material.
(3) The metal organic framework material has very high crystallinity, specific surface area and total pore volume, and can be applied to gas adsorption, gas adsorption storage and gas adsorption separation, in particular to the application in the gas adsorption storage of carbon dioxide, hydrogen, methane, carbon monoxide, nitrogen, ethane, propane and the like and the selective adsorption separation of mixed gas of carbon dioxide/methane, carbon dioxide/carbon monoxide, carbon dioxide/nitrogen, carbon dioxide/oxygen, hydrogen/carbon dioxide, hydrogen/nitrogen, methane/nitrogen, ethane/ethylene, propane/propylene and the like.
Drawings
FIG. 1 is an XRD pattern of Cu-based metal-organic framework materials synthesized in examples 1, 2, 3, 6, 7 and comparative examples 1, 2, 3, 4;
FIG. 2 is an XRD pattern of the Fe-based metal organic framework material synthesized in example 4;
FIG. 3 is an XRD pattern of the Cr-based metal organic framework material synthesized in example 5;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of sample A of example 1 after calcination at 200 ℃;
FIG. 5 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of example 2, sample B, after calcination at 200 ℃;
FIG. 6 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of example 3, sample C, after being calcined at 200 ℃;
FIG. 7 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of example 6, sample F having been calcined at 200 ℃;
FIG. 8 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of sample H of comparative example 1 after calcination at 200 ℃;
FIG. 9 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of sample I of comparative example 2 after calcination at 200 ℃;
FIG. 10 is a plot of methane adsorption for sample C of example 3.
Detailed Description
The preparation of the metal-organic framework material according to the invention is further illustrated below by means of examples, but the invention should not be construed as being limited to the following examples, wherein wt% is mass fraction.
Example 1
(1) Purification of 1,3, 5-benzenetricarboxylic acid
Adding 100.12g of crude 1,3, 5-benzenetricarboxylic acid and 2.84g of N-methylpyrrolidone into 260mL of ethanol, heating to 30 ℃ at the heating rate of 0.5 ℃/min, completely dissolving and maintaining for 30min under the stirring condition, filtering out trace 1,3, 5-benzenetricarboxylic acid and impurities, cooling the filtrate to 10 ℃ at the cooling rate of 0.5 ℃/min and maintaining for 30min, gradually precipitating and crystallizing the crude 1,3, 5-benzenetricarboxylic acid, and performing solid-liquid separation and drying to obtain the purified 1,3, 5-benzenetricarboxylic acid.
(2) Preparation of metal organic framework materials
Uniformly mixing 10.12g of purified 1,3, 5-benzenetricarboxylic acid, 8.82g of copper nitrate and 12mL of a second solvent (methanol: N, N-dimethylacetamide =0.5: 1), putting into a reaction kettle, crystallizing for 12h at 120 ℃, washing the obtained product with water after crystallization is finished, filtering, and drying the product at 200 ℃ for 12h to obtain the Cu-based metal organic framework material A with the particle size range of 4-5 microns.
Example 2
(1) Purification of 1,3, 5-benzenetricarboxylic acid
100.45g of crude 1,3, 5-benzenetricarboxylic acid and 10.12g of N-methylpyrrolidone are added into 640mL of ethanol, the temperature is increased to 100 ℃ at the heating rate of 10 ℃/min, the mixture is completely dissolved and kept for 120min under the stirring condition, then trace 1,3, 5-benzenetricarboxylic acid and impurities are filtered out, the filtrate is cooled to 25 ℃ at the cooling rate of 10 ℃/min and kept for 120min, the crude 1,3, 5-benzenetricarboxylic acid is gradually separated out and crystallized, and then solid-liquid separation and drying are carried out to obtain the purified 1,3, 5-benzenetricarboxylic acid.
(2) Preparation of metal organic framework materials
Uniformly mixing 10g of purified 1,3, 5-benzenetricarboxylic acid, 26.45g of copper nitrate and 500mL of a second solvent (methanol: N, N-dimethylacetamide =5: 1), putting into a reaction kettle, crystallizing at 120 ℃ for 12h, washing the obtained product with water after crystallization is finished, filtering, and drying the product at 200 ℃ for 12h to obtain the Cu-based metal organic framework material B with the particle size ranging from 4 micrometers to 6 micrometers.
Example 3
(1) Purification of 1,3, 5-benzenetricarboxylic acid
Adding 100.12g of crude 1,3, 5-benzenetricarboxylic acid and 4.14g of N-methylpyrrolidone into 400mL of ethanol, heating to 80 ℃ at a heating rate of 5 ℃/min, completely dissolving and maintaining for 60min under the stirring condition, filtering out trace 1,3, 5-benzenetricarboxylic acid and impurities, cooling the filtrate to 15 ℃ at a cooling rate of 5 ℃/min and maintaining for 60min, gradually precipitating and crystallizing the crude 1,3, 5-benzenetricarboxylic acid, and performing solid-liquid separation and drying to obtain the purified 1,3, 5-benzenetricarboxylic acid.
(2) Preparation of metal organic framework materials
Uniformly mixing 10.12g of purified 1,3, 5-benzenetricarboxylic acid, 23.58g of copper nitrate and 240mL of a second solvent (methanol: N, N-dimethylacetamide =1: 1), putting into a reaction kettle, crystallizing at 120 ℃ for 12h, washing the obtained product with water after crystallization is finished, filtering, and drying the product at 200 ℃ for 12h to obtain the Cu-based metal organic framework material C with the particle size range of 0.5-1.2 microns.
Example 4
(1) Purification of 1,3, 5-benzenetricarboxylic acid
Adding 100.12g of crude 1,3, 5-benzenetricarboxylic acid and 4.14g of N-methylpyrrolidone into 400mL of ethanol, heating to 80 ℃ at a heating rate of 5 ℃/min, completely dissolving and maintaining for 60min under the stirring condition, filtering out trace 1,3, 5-benzenetricarboxylic acid and impurities, cooling the filtrate to 15 ℃ at a cooling rate of 5 ℃/min and maintaining for 60min, gradually precipitating and crystallizing the crude 1,3, 5-benzenetricarboxylic acid, and performing solid-liquid separation and drying to obtain the purified 1,3, 5-benzenetricarboxylic acid.
(2) Preparation of metal organic framework materials
Uniformly mixing 10g of purified 1,3, 5-benzenetricarboxylic acid, 12.93g of ferric chloride and 300mL of a second solvent (methanol: N, N-dimethylacetamide =1: 1), putting into a reaction kettle, crystallizing for 8 hours at 180 ℃, washing the obtained product with water after crystallization is finished, filtering, and drying the product at 200 ℃ for 5 hours to obtain the Fe-based metal organic framework material D with the particle size range of 1.2-2.6 microns.
Example 5
(1) Purification of 1,3, 5-benzenetricarboxylic acid
Adding 100.12g of crude 1,3, 5-benzenetricarboxylic acid and 4.14g of N-methylpyrrolidone into 400mL of ethanol, heating to 80 ℃ at a heating rate of 5 ℃/min, completely dissolving and maintaining for 60min under the stirring condition, filtering out trace 1,3, 5-benzenetricarboxylic acid and impurities, cooling the filtrate to 15 ℃ at a cooling rate of 5 ℃/min and maintaining for 60min, gradually precipitating and crystallizing the crude 1,3, 5-benzenetricarboxylic acid, and performing solid-liquid separation and drying to obtain the purified 1,3, 5-benzenetricarboxylic acid.
(2) Preparation of metal organic framework materials
Uniformly mixing 10g of purified 1,3, 5-benzenetricarboxylic acid, 15.19g of chromium nitrate and 400mL of a second solvent (methanol: N, N-dimethylacetamide =1: 1), putting into a reaction kettle, crystallizing at 220 ℃ for 36h, washing the obtained product with water after crystallization is finished, filtering, and drying the product at 200 ℃ for 5h to obtain the Cr-based metal organic framework material E with the particle size range of 0.1-0.6 mu m.
Example 6
The preparation method of the metal organic framework material is the same as that in example 3, except that the surfactant is sodium dodecyl benzene sulfonate, and other reaction conditions and material compositions are unchanged, so that the Cu-based metal organic framework material F is obtained.
Example 7
The preparation method of the metal organic framework material is the same as that in example 3, except that the second solvent is propanol and ethylamine in a ratio of 1:1, and other reaction conditions and material compositions are unchanged, so that the Cu-based metal organic framework material G is obtained.
Comparative example 1
The metal-organic framework material was prepared as in example 3, except that N-methylpyrrolidone was not added during the purification of 1,3, 5-benzenetricarboxylic acid in step (1), and 4.14g of N-methylpyrrolidone was added during the mixing of 1,3, 5-benzenetricarboxylic acid, copper nitrate and the second solvent in step (2), to obtain a Cu-based metal-organic framework material H having a particle size ranging from 0.1 μm to 0.3. mu.m.
Comparative example 2
The preparation method of the metal organic framework material is the same as that in example 3, except that no surfactant is used, so that the Cu-based metal organic framework material I is obtained, and the particle size ranges from 0.1 μm to 0.2 μm.
Comparative example 3
The metal-organic framework material was prepared as in example 3, except that the second solvent was methanol, to give Cu-based metal-organic framework material J.
Comparative example 4
The metal-organic framework material was prepared as in example 3, except that the second solvent was N, N-dimethylacetamide, to give a Cu-based metal-organic framework material K.
TABLE 1
| Industrial 1,3, 5-benzenetricarboxylic acid purity/wt% | Purity/wt% of purified 1,3, 5-benzenetricarboxylic acid | Utilization ratio/wt% of 1,3, 5-benzenetricarboxylic acid | |
| Example 1 | 65 | 99.5 | 92 |
| Example 2 | 65 | 99.5 | 91 |
| Example 3 | 65 | 99.5 | 98 |
| Example 4 | 65 | 99.5 | 96 |
| Example 5 | 65 | 99.5 | 95 |
| Example 6 | 65 | 98.4 | 93 |
| Example 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, the purity of the crude 1,3, 5-benzenetricarboxylic acid is greatly improved to over 99.5 percent after the crude 1,3, 5-benzenetricarboxylic acid is purified, and the utilization rate of the ligand 1,3, 5-benzenetricarboxylic acid in the synthesis process of the metal organic framework material is further improved by the added surfactant and can reach 98 percent by weight.
Test example 1
The physicochemical properties of the metal-organic framework materials of examples 1 to 4, 6 to 7 and comparative examples 1 to 4 were measured, and the specific results are shown in Table 2. Wherein, the BET specific surface area and the pore volume are measured by a low-temperature liquid nitrogen adsorption method. For the determination of the relative crystallinity, the samples of examples 1-3, 6-7 and comparative examples 1-4 were purchased from the BASF company, Germany as the metal-organic framework material Cu3(BTC)2For reference (Basolite C300), the crystallinity was calculated to be 100% and determined by XRD. The sample of example 4 was calculated based on the metal organic skeleton material Fe-BTC (Basolite F300) available from BASF of Germany, with the crystallinity set to 100%, as determined by XRD.
TABLE 2 physicochemical Properties of the respective Metal-organic framework materials
| Sample (I) | BET specific surface area/m2·g-1 | Total pore volume/cm3·g-1 | Relative degree of crystallinity/%) | Thermal stability (250 ℃ C. roasting 10 h) |
| 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 | Collapse of skeleton |
| I | 862 | 0.44 | 78 | Collapse of skeleton |
| J | 956 | 0.45 | 82 | Collapse of skeleton |
| K | 929 | 0.43 | 80 | Collapse of skeleton |
As can be seen from Table 2, the metal organic framework materials prepared in examples 1-7 of the present invention have very high specific surface area, and also have higher crystallinity and better thermal stability, which are much higher than those of the metal organic framework materials prepared in comparative examples 1-4.
Test example 2
The results of the measurement of the methane adsorption amount of the metal organic framework materials of examples 1 to 3, 6, 7 and comparative examples 1 to 4 are shown in table 3.
Methane adsorption amount: high pressure adsorption of methane Using a Micromeritics HPVA-100 type adsorber. Before the sample is tested, firstly, the adsorption instrument is vacuumized for 12 hours at the temperature of 200 ℃, the vacuumizing pressure is less than 10 mu mHg, then, under the guidance of a program pressure boosting processing module, the pressure reaches 40bar and 298K, and the corresponding mass methane storage amount is obtained.
TABLE 3 methane adsorption amounts of the respective metal-organic framework materials
| Sample (I) | Methane adsorption amount/cm3/g |
| A | 185 |
| B | 189 |
| C | 204 |
| F | 175 |
| G | 181 |
| H | 140 |
| I | 106 |
| J | 127 |
| K | 135 |
The data of the effect of adsorbing methane given in table 2 further illustrate that the metal organic framework materials prepared in examples 1-3, 6 and 7 of the present invention have higher methane adsorption amount.
FIG. 1 is an XRD pattern of Cu-based metal-organic framework materials synthesized in examples 1, 2, 3, 6, 7 and comparative examples 1, 2, 3, 4; according to the characteristic peak, the metal organic framework material Cu synthesized by the method3(BTC)2. FIG. 2 is an XRD spectrum of the Fe-based metal organic framework material synthesized in example 4, and it can be seen from the characteristic peaks that the metal organic framework material Fe-BTC is synthesized by the present invention; FIG. 3 is an XRD spectrum of the Cr-based metal organic framework material synthesized in example 5, and it can be seen from the characteristic peaks that the metal organic framework material synthesized by the present invention, Cr-BTC.
FIG. 4 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of sample A of example 1 after calcination at 200 ℃; FIG. 5 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of example 2, sample B, after calcination at 200 ℃; FIG. 6 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of example 3, sample C, after being calcined at 200 ℃; FIG. 7 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of example 6, sample F having been calcined at 200 ℃; FIG. 8 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of sample H of comparative example 1 after calcination at 200 ℃; FIG. 9 is a Scanning Electron Microscope (SEM) image of a metal-organic framework material of sample I of comparative example 2 after calcination at 200 ℃;
by comparison, it can be seen that the metal organic framework materials of examples 1,3 and 6 still maintain the complete morphology and framework structure after being baked at 200 ℃ for 10h, while the metal organic framework materials of comparative examples 1 and 2 completely collapse after being baked at 200 ℃ for 10h, and the morphology cannot be distinguished.
Claims (29)
1. The preparation method of the metal organic framework material is characterized by comprising the following steps:
(1) adding crude 1,3, 5-benzene tricarboxylic acid into a first solvent for recrystallization to obtain purified 1,3, 5-benzene tricarboxylic acid, wherein the recrystallization comprises the steps of heating up for dissolution and cooling down for precipitation, and a surfactant is introduced before the crude 1,3, 5-benzene tricarboxylic acid is heated up for dissolution, in the heating up for dissolution and/or after the heating up for dissolution and before the cooling down for precipitation; the surfactant is one or more of N-methyl pyrrolidone and sodium dodecyl benzene sulfonate;
(2) uniformly mixing the purified 1,3, 5-benzene tricarboxylic acid, metal salt and a second solvent, and then crystallizing, separating, washing and drying to obtain the metal organic framework material; the second solvent is a mixed solution containing an alcohol solvent and a nitrogen-containing compound solvent.
2. The method of claim 1, wherein: the weight ratio of the crude 1,3, 5-benzene tricarboxylic acid, the surfactant and the first solvent is 1 (0.01-0.5) to 1-50.
3. The method of claim 1, wherein: the weight ratio of the crude 1,3, 5-benzene tricarboxylic acid, the surfactant and the first solvent is 1 (0.02-0.1) to 2-5.
4. The method of claim 1, wherein: the surfactant is N-methyl pyrrolidone.
5. The method of claim 1, wherein: the first solvent is a lower alcohol.
6. The method of claim 5, wherein: the first solvent is one or more of methanol, ethanol, propanol, butanol and glycol.
7. The method of claim 6, wherein: the first solvent is ethanol.
8. The method of claim 1, wherein: the purity of the crude 1,3, 5-benzene tricarboxylic acid is 50wt% -70 wt%.
9. The method of claim 1, wherein: the purity of the purified 1,3, 5-benzene tricarboxylic acid is 80.00wt% -99.99 wt%.
10. The method of claim 1, wherein: the purity of the purified 1,3, 5-benzene tricarboxylic acid is 90.0wt% -99.9 wt%.
11. The method of claim 1, wherein: in the step (1), the heating dissolution comprises the following specific steps: raising the temperature to 30-100 ℃ at the heating rate of 0.5-10 ℃/min and keeping the temperature for 30-2 h.
12. The method of claim 1, wherein: in the step (1), the specific steps of cooling and precipitating are as follows: cooling to 10-25 ℃ at the cooling rate of 0.5-10 ℃/min and keeping for 30 min-2 h.
13. The method of claim 1, wherein: the recrystallization further comprises: and after cooling and precipitation, carrying out separation, washing and drying.
14. The method of claim 1, wherein: the metal salt is one or more of Pd, Pt, Ru, Ag, Ni, Cu, Au, Li, Rh, Ir, Ce, Sc, Fe, Mo, Co and W, and the metal salt is one or more of sulfate, nitrate, acetate, carbonate, chloride and bromide of the metal elements.
15. The method of claim 14, wherein: the metal salt is copper nitrate or ferric chloride.
16. The method of claim 1, wherein: the molar ratio of the metal ions to the 1,3, 5-benzene tricarboxylic acid in the metal salt is (0.5-5): 1, and the weight ratio of the 1,3, 5-benzene tricarboxylic acid to the second solvent is 1: (0.5-100).
17. The method of claim 16, wherein: the molar ratio of the metal ions to the 1,3, 5-benzene tricarboxylic acid in the metal salt is (0.9-3): 1, and the weight ratio of the 1,3, 5-benzene tricarboxylic acid to the second solvent is 1: (1-40).
18. The method of claim 1, wherein: the weight ratio of the alcohol solvent to the nitrogen-containing compound solvent is (0.1-10): 1.
19. The method of claim 1, wherein: the weight ratio of the alcohol solvent to the nitrogen-containing compound solvent is (0.5-5): 1.
20. A method according to claim 1 or 18, characterized by: the alcohol solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, 3-methyl-2-butanol, hexanol, 2-ethyl butanol, 2-methyl amyl alcohol, heptanol, octanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, cyclopentanol, cyclohexanol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol and pentaerythritol;
the nitrogen-containing compound solvent is one or more of nitrobenzene, acetonitrile, propionitrile, succinonitrile, methylamine, dimethylamine, ethylamine, triethylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, tributylamine, aniline, cyclohexylamine, pyrrole, pyridine, quinoline, formamide, N-methylformamide, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-methylacetamide and N-methylpropionamide.
21. A method according to claim 1 or 18, characterized by: the alcohol solvent is one or more of methanol, ethanol, propanol, butanol, isobutanol, hexanol, 2-ethyl butanol, heptanol, cyclopentanol, butanediol and pentaerythritol;
the nitrogen-containing compound solvent is one or more of nitrobenzene, ethylamine, tributylamine, pyrrole, pyridine, quinoline, N-dimethylformamide, N-diethylformamide and N-methylpropionamide.
22. A method according to claim 1 or 18, characterized by: the alcohol solvent is methanol; the nitrogen-containing compound solvent is N, N-dimethylacetamide.
23. The method of claim 1, wherein: in the step (2), the crystallization temperature is 80-300 ℃, the crystallization time is 5-40 h, the drying temperature is 100-300 ℃, and the drying time is 5-24 h.
24. A metal organic framework material prepared according to the method of any one of claims 1 to 23.
25. A metal-organic framework material according to claim 24, characterized in that: the properties of the metal-organic framework material are as follows: the specific surface area is 500m2/g～3000m2(g) total pore volume of 0.3cm3/g～0.9cm3/g。
26. A metal-organic framework material according to claim 24, characterized in that: the properties of the metal-organic framework material are as follows: specific surface area of 1000m2/g～2500m2(g) total pore volume of 0.4cm3/g～0.7cm3/g。
27. A metal-organic framework material according to claim 24, characterized in that: the average grain diameter of the metal organic framework material is 0.1-10 mu m.
28. A metal-organic framework material according to claim 24, characterized in that: the average grain diameter of the metal organic framework material is 0.5-6 mu m.
29. A metal-organic framework material according to claim 24, characterized in that: the relative crystallinity of the metal organic framework material is 95-100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610736797.0A CN107774329B (en) | 2016-08-29 | 2016-08-29 | Metal organic framework material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610736797.0A CN107774329B (en) | 2016-08-29 | 2016-08-29 | Metal organic framework material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107774329A CN107774329A (en) | 2018-03-09 |
| CN107774329B true CN107774329B (en) | 2020-03-17 |
Family
ID=61439744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610736797.0A Active CN107774329B (en) | 2016-08-29 | 2016-08-29 | Metal organic framework material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107774329B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554454B (en) * | 2018-03-12 | 2019-11-15 | 华南理工大学 | A kind of metal-organic framework materials being fixed with Platinum Nanoparticles prepare purification process and its application |
| CN109659571B (en) * | 2019-01-29 | 2022-02-01 | 东华大学 | Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor |
| CN112349916B (en) * | 2020-11-16 | 2021-09-14 | 大连理工大学 | Iron-doped ZIF8 and Ce-based metal organic framework composite electrocatalyst and preparation method and application thereof |
| CN114682223A (en) * | 2020-12-30 | 2022-07-01 | 中国石油化工股份有限公司 | Metal-loaded modified Cu-BTC material and preparation method thereof |
| CN115582015A (en) * | 2022-10-13 | 2023-01-10 | 苏州大学 | Heterogeneous catalytic deoxidation method |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2278267T3 (en) * | 2004-12-15 | 2007-08-01 | Saudi Basic Industries Corporation | PROCESS TO PREPARE PURIFIED TEREFTALIC ACID. |
| CN101121655A (en) * | 2007-08-30 | 2008-02-13 | 洪芳柏 | Technique for purifying crude terephthalic acid |
| US9120080B2 (en) * | 2010-02-10 | 2015-09-01 | The Board Of Regents Of The University Of Texas System | Acetylene storage using metal-organic frameworks with open metal sites |
| US10182593B2 (en) * | 2011-08-01 | 2019-01-22 | Massachusetts Institute Of Technology | Porous catalytic matrices for elimination of toxicants found in tobacco combustion products |
| US9307790B2 (en) * | 2011-08-01 | 2016-04-12 | Massachusetts Institute Of Technology | Porous catalytic matrices for elimination of toxicants found in tobacco combustion products |
| US8883676B1 (en) * | 2013-01-08 | 2014-11-11 | The United States Of America As Represented By The Secretary Of The Army | Removal of toxic chemicals using metal-organic frameworks (MOFs) post-treated via plasma-enhanced chemical vapor deposition (PECVD) with fluorocarbons |
| CN104415737A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院大连化学物理研究所 | Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation |
| CN104892518B (en) * | 2014-03-05 | 2018-04-27 | 中国科学院大连化学物理研究所 | The preparation method and applications of porous nano metal organic framework materials |
| CN104974036B (en) * | 2014-04-11 | 2016-10-05 | 中国石化扬子石油化工有限公司 | A kind of method of purification of thick trimesic acid |
| CN104959115A (en) * | 2015-06-11 | 2015-10-07 | 中国科学院山西煤炭化学研究所 | Preparation method of nanoscale metal-organic framework compound |
| CN105312028A (en) * | 2015-11-20 | 2016-02-10 | 华南理工大学 | Zinc and copper bi-metal organic framework material and preparation method and application thereof |
| CN105727736B (en) * | 2016-01-28 | 2018-05-11 | 内蒙古大学 | Method of the catalyst for scrubbing CO_2 is prepared with metal-organic framework materials |
-
2016
- 2016-08-29 CN CN201610736797.0A patent/CN107774329B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107774329A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109384935B (en) | Metal organic framework material and preparation method thereof | |
| CN107774329B (en) | Metal organic framework material and preparation method thereof | |
| Samarasinghe et al. | Tailoring CO2/CH4 separation properties of mixed-matrix membranes via combined use of two-and three-dimensional metal-organic frameworks | |
| CN109384665A (en) | One kind containing bimetallic metal-organic framework materials and preparation method thereof | |
| Vo et al. | Formation of structural defects within UiO-66 (Zr)-(OH) 2 framework for enhanced CO2 adsorption using a microwave-assisted continuous-flow tubular reactor | |
| Zhang et al. | Fabrication of highly (110)-Oriented ZIF-8 membrane at low temperature using nanosheet seed layer | |
| US9067956B2 (en) | Zeolite porous metal bis(imidazole) coordination polymers and preparation method thereof | |
| CN106905536B (en) | Method for rapidly synthesizing hierarchical pore ZIF-8 material | |
| Azizi et al. | Fabrication and characterization of highly efficient three component CuBTC/graphene oxide/PSF membrane for gas separation application | |
| Huang et al. | Preparation of novel metal-carboxylate system MOF membrane for gas separation | |
| Wang et al. | Synthesis of ZIF-8 in a deep eutectic solvent using cooling-induced crystallisation | |
| Peng et al. | Application of metal organic frameworks M (bdc)(ted) 0.5 (M= Co, Zn, Ni, Cu) in the oxidation of benzyl alcohol | |
| Liu et al. | Bottom-up synthesis of two-dimensional composite via CuBDC-ns growth on multilayered MoS2 to boost CO2 permeability and selectivity in Pebax-based mixed matrix membranes | |
| Peralta et al. | Synthesis and adsorption properties of ZIF-76 isomorphs | |
| CN106832323B (en) | Method for rapidly synthesizing hierarchical pore HKUST-1 material by using dual-function template method | |
| Xia et al. | A long-lasting TIF-4 MOF glass membrane for selective CO2 separation | |
| CN113583252B (en) | Microporous metal organic framework Cu (Qc) 2 Preparation method of (1) | |
| JP6221910B2 (en) | Metal complex and method for producing the same | |
| CN111729518A (en) | Preparation method and application of ligand-doped metal organic framework hybrid ZIF-8membrane | |
| CN110639474A (en) | Adsorbent for separating propylene and propane and preparation method thereof | |
| Han et al. | CO2 separation performance for PIM based mixed matrix membranes embedded by superbase ionic liquids | |
| CN109880111B (en) | Catalyst for synthesizing polyether amine and preparation method thereof | |
| CN111777769B (en) | Metal organic framework material for efficiently separating mixed gas and preparation method and application thereof | |
| EP2907817B1 (en) | Method for preparing cu-btc and nano-cu-btc | |
| KR20200047352A (en) | Nanoparticle comprising modulated zeolitic imidazolate framework and method of preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |