CN116063688B - Flexible metal-organic framework material and preparation method thereof - Google Patents
Flexible metal-organic framework material and preparation method thereof Download PDFInfo
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- CN116063688B CN116063688B CN202111284115.4A CN202111284115A CN116063688B CN 116063688 B CN116063688 B CN 116063688B CN 202111284115 A CN202111284115 A CN 202111284115A CN 116063688 B CN116063688 B CN 116063688B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 297
- 239000000463 material Substances 0.000 title claims abstract description 263
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 167
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000013110 organic ligand Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 28
- 238000006467 substitution reaction Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004729 solvothermal method Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- -1 aluminum ion Chemical class 0.000 description 63
- 238000010521 absorption reaction Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 238000001179 sorption measurement Methods 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 101100131043 Oryza sativa subsp. japonica MOF1 gene Proteins 0.000 description 19
- 238000001144 powder X-ray diffraction data Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 12
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 229910001430 chromium ion Inorganic materials 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 229910001429 cobalt ion Inorganic materials 0.000 description 10
- 229910001456 vanadium ion Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 8
- 229910001422 barium ion Inorganic materials 0.000 description 8
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- 229910001437 manganese ion Inorganic materials 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- 229910001453 nickel ion Inorganic materials 0.000 description 8
- 229910001427 strontium ion Inorganic materials 0.000 description 8
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 8
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 8
- 239000001530 fumaric acid Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000010413 mother solution Substances 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052735 hafnium Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052691 Erbium Inorganic materials 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 4
- 229920002266 Pluriol® Polymers 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229910001423 beryllium ion Inorganic materials 0.000 description 4
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 4
- 229910000071 diazene Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910001449 indium ion Inorganic materials 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 description 2
- NETRDQTXSOQBLU-UHFFFAOYSA-D O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[V+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[V+5] Chemical compound O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[V+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[V+5] NETRDQTXSOQBLU-UHFFFAOYSA-D 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- MMXZSJMASHPLLR-UHFFFAOYSA-N pyrroloquinoline quinone Chemical compound C12=C(C(O)=O)C=C(C(O)=O)N=C2C(=O)C(=O)C2=C1NC(C(=O)O)=C2 MMXZSJMASHPLLR-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
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- ZJQZWNLKRBUEKX-UHFFFAOYSA-N 2,5-dianilinoterephthalic acid Chemical compound OC(=O)C=1C=C(NC=2C=CC=CC=2)C(C(=O)O)=CC=1NC1=CC=CC=C1 ZJQZWNLKRBUEKX-UHFFFAOYSA-N 0.000 description 1
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- ZHGGHNZZJCJQSL-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxymethyl]propanedioic acid Chemical compound CCOCCOCCOCC(C(O)=O)C(O)=O ZHGGHNZZJCJQSL-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- IIQLVLWFQUUZII-UHFFFAOYSA-N 2-amino-5-(4-amino-3-carboxyphenyl)benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1C1=CC=C(N)C(C(O)=O)=C1 IIQLVLWFQUUZII-UHFFFAOYSA-N 0.000 description 1
- RTZDLIFCPWVQEZ-UHFFFAOYSA-N 2-benzoylbenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(=O)C1=CC=CC=C1 RTZDLIFCPWVQEZ-UHFFFAOYSA-N 0.000 description 1
- HSBSUGYTMJWPAX-UHFFFAOYSA-N 2-hexenedioic acid Chemical compound OC(=O)CCC=CC(O)=O HSBSUGYTMJWPAX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The application discloses a flexible metal-organic framework material and a preparation method thereof. The preparation method comprises the following steps: s1: providing a rigid metal-organic framework material; wherein the rigid metal-organic framework material is formed from at least one initial metal ion and an organic ligand coordinated to the initial metal ion; s2: replacing at least one initial metal ion in the rigid metal-organic framework material with at least one replacement metal ion, and performing metal ion replacement reaction on the rigid metal-organic framework material to obtain a flexible metal-organic framework material; wherein the flexible metal-organic framework material comprises a replacement metal ion and an organic ligand coordinated to the replacement metal ion. The preparation method of the flexible metal-organic framework material has the advantages of simple process, low production cost, predictable product performance and the like, and is suitable for industrialized mass production of the flexible metal-organic framework material.
Description
Technical Field
The application relates to the field of metal-organic framework material synthesis, in particular to a flexible metal-organic framework material and a preparation method thereof.
Background
Metal-organic framework (Metal-Organic Frameworks; MOFs) materials are a class of crystalline materials having an ordered structure, typically formed by coordination bonding of at least one Metal ion and at least one at least bidentate organic ligand. The metal-organic framework material thus has a rich variety of structural morphologies due to the very wide variety of metal ions and at least bidentate organic ligands forming the metal-organic framework material. The structure of the metal-organic framework material is classified into a rigid structure and a flexible structure according to whether it can be reversibly deformed under external stimulus (such as heat, light, pressure, or interaction between small molecules of external guests and the framework structure). The metal-organic framework material with the rigid structure does not generate any structural deformation under the external stimulus, and the metal-organic framework material with the flexible structure generates reversible structural deformation such as expansion, shrinkage, deflection and the like under the external stimulus. The metal-organic framework material with the flexible structure has high application value in the fields such as gas adsorption storage, mixed gas separation, sensor technology and the like. Such metal-organic framework materials having Flexible structures have been described in detail in reference "Flexible metal-organic frameworks, a.schenecmann et al, chem.soc.rev.,43 (2014), pages 6062-6096".
There are some methods for synthesizing metal-organic framework materials with flexible structures, however, these methods generally have one or more problems of excessively high synthesis cost, excessively complex synthesis steps, severe synthesis conditions, easiness in structural collapse of the metal-organic framework materials, incapacity of predicting the performance of the materials before synthesizing the metal-organic framework materials, and the like, and therefore, these methods cannot be industrially popularized.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the application.
The application mainly aims to provide a flexible metal-organic framework material and a preparation method thereof, which can solve the problem that the existing preparation method of the flexible metal-organic framework material cannot be popularized in an industrialized way.
In order to achieve the above object, the embodiment of the present application provides a method for preparing a flexible metal-organic framework material, including:
S1: providing a rigid metal-organic framework material; wherein the rigid metal-organic framework material is formed from at least one initial metal ion and an organic ligand coordinated to the initial metal ion;
S2: replacing at least one initial metal ion in the rigid metal-organic framework material with at least one replacement metal ion, and performing metal ion replacement reaction on the rigid metal-organic framework material to obtain a flexible metal-organic framework material;
Wherein the flexible metal-organic framework material comprises a replacement metal ion and an organic ligand coordinated to the replacement metal ion.
Preferably, the flexible metal-organic framework material further comprises an initial metal ion and an organic ligand coordinated to the initial metal ion.
Preferably, the rigid metal-organic framework material comprises one initial metal ion and the replacement metal ion is one.
Preferably, the metal ion substitution reaction is a hydrothermal synthesis reaction or a solvothermal synthesis reaction.
Preferably, the preparation method further comprises: after the step S2 of the process, the process proceeds,
S3: and (2) separating the flexible metal-organic framework material from the reaction liquid containing the flexible metal-organic framework material obtained in the step (S2), and drying to obtain a flexible metal-organic framework material product.
Preferably, the initial metal ion is selected from one or more of magnesium ion, calcium ion, strontium ion, zirconium ion, chromium ion, cobalt ion, titanium ion, vanadium ion, aluminum ion, iron ion, zinc ion, copper ion, barium ion, iridium ion, nickel ion, cadmium ion, and the like.
Preferably, the replacement metal ion is selected from one or more of beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, titanium ion, zirconium ion, hafnium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, cadmium ion, aluminum ion, indium ion, lanthanum ion, cerium ion, neodymium ion, samarium ion, europium ion, erbium ion, tungsten ion, and the initial metal ion is different from the replacement metal ion.
Preferably, the initial metal ion is an aluminum ion, and the replacement metal ion is one or more selected from iron ion, chromium ion, titanium ion, manganese ion and vanadium ion.
Preferably, the initial metal ion is zirconium ion, and the replacement metal ion is one or more of cobalt ion, chromium ion, iron ion, titanium ion and hafnium ion.
Preferably, the initial ion is chromium ion, and the replacement metal ion is one or more of aluminum ion, iron ion, titanium ion, manganese ion, tungsten ion and vanadium ion.
Preferably, the initial ion is one of magnesium ion, calcium ion, strontium ion, barium ion, zinc ion, copper ion, cobalt ion, iridium ion, nickel ion, cadmium ion, the replacement metal ion is selected from one or more of beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, titanium ion, zirconium ion, hafnium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, cadmium ion, aluminum ion, indium ion, lanthanum ion, cerium ion, neodymium ion, samarium ion, europium ion, erbium ion, tungsten ion, and the initial metal ion is different from the replacement metal ion.
Preferably, in step S2, the ratio of the total moles of the replacement metal ions employed to the total moles of the initial metal ions contained in the rigid metal-organic framework material is (0.1 to 2): 1.
Preferably, the reaction temperature of the metal ion substitution reaction is 0 ℃ to 250 ℃.
Preferably, the reaction pressure of the metal ion substitution reaction is 0.1bar to 20bar.
Preferably, the reaction time of the metal ion substitution reaction is 2 to 96 hours.
Preferably, the metal ion substitution reaction is carried out under stirring conditions at a stirring speed of not more than 1000rpm.
Preferably, the metal ion replacement reaction is carried out in the presence of a solvent selected from one or more of water, methanol, ethanol, propanol, butanol, pentanol, hexanol, dimethylformamide, dimethylacetamide, diethylformamide, dimethylsulfoxide, N-methylpyrrolidone, acetonitrile, toluene, chlorobenzene, methylethylketone, tetrahydrofuran, ethyl acetate.
The embodiment of the application also provides a flexible metal-organic framework material, which is obtained by the preparation method.
According to the preparation method of the flexible metal-organic framework material, provided by the embodiment of the application, the metal-organic framework material with the rigid structure is converted into the metal-organic framework material with the flexible structure in a metal ion substitution mode, so that the following beneficial technical effects can be obtained:
1. The preparation method of the embodiment of the application does not need to adopt flexible at least bidentate organic ligands, does not involve the functional modification of the organic ligands which participate in the formation of the metal-organic framework material, can obtain the metal-organic framework material with a flexible structure by only carrying out one-step metal ion replacement reaction after obtaining the metal-organic framework material with a rigid structure, and has the advantages of simple process and low production cost;
2. the preparation method of the embodiment of the application does not involve the functional modification of the metal-organic framework material under the severe reaction condition, and can avoid the structural collapse of the metal-organic framework material under the severe reaction condition;
3. The flexible metal-organic framework material obtained by the preparation method provided by the embodiment of the application does not belong to metal-organic framework materials with two-dimensional stacked structures or three-dimensional pore interpenetrating structures, so that the occurrence of the unexpected situation that the prepared metal-organic framework material cannot show the two-dimensional stacked structures or the three-dimensional pore interpenetrating structures can be avoided;
4. The preparation method of the embodiment of the application is based on the metal-organic framework material with the rigid structure and known performance, and the metal-organic framework material with the flexible structure can be obtained by proper transformation, so that the performance of the obtained flexible metal-organic framework material is improved to a certain extent compared with that of the original rigid metal-organic framework material, and the performance of the flexible metal-organic framework material can be predicted before the flexible metal-organic framework material is obtained;
In summary, the method for preparing the flexible metal-organic framework material provided by the embodiment of the application is suitable for industrialized mass production of the flexible metal-organic framework material.
Other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a powder XRD pattern of MOF 1-stiffness prepared in example 1 of the present application before and after the first water absorption;
FIG. 2 is a powder XRD pattern of MOF1 prepared in example 1 of the present application before and after the first water absorption;
FIG. 3 is a powder XRD pattern of MOF1 prepared in example 1 of the present application before and after the first water absorption and before and after the second water absorption;
FIG. 4 is a powder XRD pattern of MOF 2-stiffness prepared in example 2 of the present application, before and after the first water absorption;
FIG. 5 is a powder XRD pattern of MOF2 prepared in example 2 of the present application before and after the first water absorption;
FIG. 6 is a powder XRD pattern of MOF2 prepared in example 2 of the present application before and after the first water absorption and before and after the second water absorption;
FIG. 7 is a powder XRD pattern of MOF 3-stiffness prepared in example 3 of the present application, before and after the first water absorption;
FIG. 8 is a powder XRD pattern of MOF3 prepared in example 3 of the present application, before and after the first water absorption;
FIG. 9 is a graph showing the rigidity of MOF 1-and the water vapor adsorption curve of MOF1 obtained in example 1 of the present application;
FIG. 10 is a graph showing the rigidity of MOF2 and the water vapor adsorption curve of MOF2 obtained in example 2 of the present application;
FIG. 11 is a graph showing the rigidity of MOF3 and the water vapor adsorption curve of MOF3 obtained in example 3 of the present application.
The achievement of the objects, functional features and advantages of the present application will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The ideas adopted by the current design of metal-organic frameworks (MOFs) with flexible structures mainly comprise the following three types:
1. The use of flexible at least bidentate organic ligands is involved in the construction of metal-organic framework (MOFs) materials: the method mainly utilizes the characteristic that the flexible at least bidentate organic ligand is easy to generate configuration change to drive the whole metal-organic framework to generate deformation, wherein the flexibility of the at least bidentate organic ligand is mainly brought by rotation or configuration change of chemical bonds (such as C-C bonds) in the at least bidentate organic ligand;
2. The functionalized and modified organic ligand is used for participating in the construction of metal-organic frameworks (MOFs) materials: in this method, the organic ligands employed for the functionalization may be either flexible or rigid; functional modification generally refers to grafting certain photosensitive organic groups or thermosensitive organic groups onto an organic ligand to obtain an organic ligand with photosensitive organic groups or thermosensitive organic groups (functional groups); the photosensitive organic groups or thermosensitive organic groups on the organic ligand can be reversibly deformed to a certain extent after being stimulated by external light, heat and the like; reversible deformation of functional groups on these organic ligands can bring about reversible changes in the structure of the metal-organic frameworks in terms of pore size, pore volume, and the like;
3. Constructing a metal-organic framework material having two dimensions stacked on top of each other or a metal-organic framework material having three dimensions interpenetrating each other through the pores: when the two metal-organic framework materials adsorb and store external gas or liquid small molecules, the stacking structure of the two metal-organic framework materials is gradually opened along with the gradual increase of the amount of the adsorbed and stored molecules, and the interpenetration structures are gradually separated from each other; moreover, this structural change is reversible, and as adsorbed and stored molecules leave the metal-organic framework material, the structure will change back to a stacked or interpenetrating form.
However, all three of the above methods for designing metal-organic frameworks (MOFs) with flexible structures have certain drawbacks, including:
1. Flexible at least bidentate organic ligands are either costly or require separate synthesis; these problems result in too high synthesis cost or too complex synthesis steps of the metal-organic framework material with the flexible structure, and large-scale mass production popularization cannot be performed;
2. The functionalization reformation of organic ligands involves two reformation modes: a) Firstly, carrying out functional modification on an organic ligand, and then synthesizing a metal-organic framework material by utilizing the organic ligand after the functional modification; b) Firstly, synthesizing a metal-organic framework material, and then performing functional modification on an organic ligand in the synthesized metal-organic framework material; wherein, the mode a) needs an independent organic synthesis flow of the organic ligand which is functionally transformed, so that the synthesis complexity of the metal-organic framework material is increased, and the synthesis cost of the metal-organic framework material is greatly increased; b) The mode relates to the functional modification of the metal-organic framework material under the severe reaction condition, and most of the metal-organic framework material can generate structural collapse under the severe reaction condition, so the application range of the method is very narrow;
3. The main problem of synthesizing the metal-organic framework material with the flexible structure by adopting a two-dimensional stacking or three-dimensional pore channel interpenetration method is that the metal-organic framework material cannot be effectively designed before the material is synthesized, that is, whether the synthesized metal-organic framework material can finally show a two-dimensional stacking structure or a three-dimensional pore channel interpenetration structure has certain 'unexpected' performance, and the material generated by 'unexpected' can not be industrially popularized;
In addition, the three design methods have a common defect that at the beginning of design/synthesis, the performances of the finally obtained metal-organic framework material (such as the adsorption performance of the material on gas/liquid small molecules, the separation capability of the material on mixed gas/liquid and the like) are unpredictable, and the finally obtained metal-organic framework material has good possibility and poor possibility; if the ratio of the product with poor performance in the synthesized metal-organic framework material is larger, a great amount of resource waste and great increase of cost are caused, and further, the metal-organic framework material with a flexible structure is caused to have great increase of resource waste and great increase of cost in the commercialization process.
In order to solve the problem that the existing preparation method of metal-organic frameworks (MOFs) with flexible structures cannot be industrially popularized, the embodiment of the application provides a method for preparing a flexible metal-organic frameworks (MOFs) material, which comprises the following steps:
S1: providing a rigid metal-organic framework material (i.e., a metal-organic framework material having a rigid structure); here, the rigid metal-organic framework material is formed from one or more initial metal ions and an organic ligand coordinated to the initial metal ions;
s2: replacing one or more initial metal ions in the rigid metal-organic framework material with one or more replacement metal ions, and performing metal ion replacement reaction on the rigid metal-organic framework material to obtain a metal-organic framework material with a flexible structure, namely the flexible metal-organic framework material;
Wherein the flexible metal-organic framework material contains one or more replacing metal ions and an organic ligand coordinated with the replacing metal ions.
According to the method for preparing the flexible metal-organic frameworks (MOFs) material, disclosed by the embodiment of the application, the metal-organic frameworks with the rigid structure are converted into the metal-organic frameworks with the flexible structure in a metal ion substitution mode, so that the following beneficial technical effects can be obtained:
1. The preparation method of the embodiment of the application does not need to adopt a flexible at least bidentate organic ligand, and the metal-organic framework material with the rigid structure in the step S1 can be prepared by adopting the rigid organic ligand, so that the preparation method of the embodiment of the application does not need to independently synthesize or purchase the flexible at least bidentate organic ligand; in addition, the preparation method of the embodiment of the application does not involve the functional modification of the organic ligand which participates in the formation of the metal-organic framework material, so that an independent organic synthesis flow of the organic ligand which is functionally modified is not needed; the preparation method of the embodiment of the application can obtain the metal-organic framework material with the flexible structure by only carrying out one-step metal ion replacement reaction after obtaining the metal-organic framework material with the rigid structure, and has the advantages of simple process and low production cost as the complex organic ligand synthesis process or the organic ligand functional modification process is not involved; furthermore, the preparation method of the embodiment of the application does not need to use various organic synthesis equipment when synthesizing the flexible metal-organic framework material, and can further reduce the production cost of the flexible metal-organic framework material;
2. the preparation method of the embodiment of the application does not involve the functional modification of the metal-organic framework material under the severe reaction condition, and can avoid the structural collapse of the metal-organic framework material under the severe reaction condition;
3. The flexible metal-organic framework material obtained by the preparation method provided by the embodiment of the application does not belong to metal-organic framework materials with two-dimensional stacked structures or three-dimensional pore interpenetrating structures, so that the occurrence of the unexpected situation that the prepared metal-organic framework material cannot show the two-dimensional stacked structures or the three-dimensional pore interpenetrating structures can be avoided;
4. The preparation method of the embodiment of the application can be properly modified based on the known metal-organic framework material with a rigid structure, so that the modified metal-organic framework material has a flexible structure; because the performance of the original material (metal-organic framework material with a rigid structure) is known, the preparation method of the embodiment of the application does not damage the original performance of the original material, and the performance of the material obtained after modification is generally improved to a certain extent compared with that of the original material due to the structural flexibility of the material, so that the final performance of the material can be predicted to a certain extent at the beginning of material synthesis; for example, the original metal-organic framework material has a rigid structure, and the adsorption amount of the original metal-organic framework material to the guest molecules is constant, while the metal-organic framework material with a flexible structure obtained by the preparation method of the embodiment of the application can contain more guest molecules due to structural deformation in the process of adsorbing the guest molecules, so that a certain improvement in adsorption performance can be obtained, and the adsorption performance of the metal-organic framework material with a flexible structure can be improved by 10% to 40% relative to that of the original metal-organic framework material with a rigid structure.
Therefore, the method for preparing the flexible metal-organic frameworks (MOFs) solves the problems existing in the existing method for preparing the flexible metal-organic frameworks, and is suitable for industrialized mass production of the flexible metal-organic frameworks.
In embodiments of the present application, the flexible metal-organic framework material may further comprise one or more initial metal ions and an organic ligand that coordinates to the initial metal ions.
In the step S2, the replacement metal ions can completely replace the initial metal ions, and then the metal ions in the obtained flexible metal-organic framework are completely composed of the replacement metal ions; the replacement metal ion may not completely replace the initial metal ion, and the obtained flexible metal-organic framework contains two or more metal ions, namely one or more replacement metal ions and the initial metal ion.
In an embodiment of the present application, the rigid metal-organic framework material may contain only one kind of initial metal ion, and the replacing metal ion used to replace the one kind of initial metal ion in step S2 may be only one kind.
In the embodiment of the present application, the metal ion substitution reaction may be a hydrothermal synthesis reaction or a solvothermal synthesis reaction.
In an embodiment of the present application, the step S2 may include: mixing the rigid metal-organic framework material provided in the step S1 with one or more metal-replacing precursors and a solvent to obtain a mixed solution containing one or more metal-replacing ions, and carrying out hydrothermal synthesis reaction or solvothermal synthesis reaction on the mixed solution to replace one or more initial metal ions in the rigid metal-organic framework material with one or more metal-replacing ions so as to obtain the flexible metal-organic framework material.
In an embodiment of the present application, the method for preparing a flexible metal-organic framework material may further include: after the step S2 of the process, the process proceeds,
S3: separating the flexible metal-organic framework material;
The method specifically comprises the following steps: and (3) separating the flexible metal-organic framework material from the reaction liquid containing the flexible metal-organic framework material obtained in the step (S2), and drying the flexible metal-organic framework material to obtain a flexible metal-organic framework material product.
In an embodiment of the present application, the method for preparing a flexible metal-organic framework material may include:
S1: providing a rigid metal-organic framework material (i.e., a metal-organic framework material having a rigid structure); here, the rigid metal-organic framework material is formed from one or more initial metal ions and an organic ligand coordinated to the initial metal ions;
s2: replacing one or more initial metal ions in the rigid metal-organic framework material with one or more replacement metal ions, and performing metal ion replacement reaction on the rigid metal-organic framework material to obtain a metal-organic framework material with a flexible structure, namely the flexible metal-organic framework material;
S3: separating the flexible metal-organic framework material from the reaction liquid containing the flexible metal-organic framework material obtained in the step S2, and drying the flexible metal-organic framework material to obtain a flexible metal-organic framework material product;
Wherein the flexible metal-organic framework material contains one or more replacing metal ions and an organic ligand coordinated with the replacing metal ions.
In an embodiment of the present application, the initial metal ion contained in the rigid metal-organic framework material may be selected from any one or more of magnesium ion (Mg 2+), calcium ion Ca 2+), strontium ion (Sr 2+), zirconium ion (Zr 4+), chromium ion (Cr 3+), cobalt ion (Co 3 +,Co2+), titanium ion (Ti 4+), vanadium ion (V 4+,V3+,V2+), aluminum ion (Al 3+), iron ion (Fe 3+,Fe2+), zinc ion (Zn 2 +), copper ion (Cu 2+,Cu+), barium ion (Ba 2+), iridium ion (Ir 3+), nickel ion (Ni 2+,Ni+), cadmium ion (Cd 2+).
In an embodiment of the present application, the replacement metal ion employed in step S2 may Be selected from beryllium ion (Be 2+), magnesium ion (Mg 2+), calcium ion (Ca 2+), strontium ion (Sr 2+), Barium ion (Ba 2+), titanium ion (Ti 4+), zirconium ion (Zr 4+), hafnium ion (Hf 4+), Vanadium ions (V 4+,V3+,V2+), chromium ions (Cr 3+), manganese ions (Mn 3+,Mn2+), iron ions (Fe 3+,Fe2+), Cobalt ions (Co 3+,Co2+), nickel ions (Ni 2+,Ni+), copper ions (Cu 2+,Cu+), zinc ions (Zn 2+), Cadmium ions (Cd 2+), aluminum ions (Al 3+), indium ions (In 3+), lanthanum ions (La 3+), Cerium ions (Ce 3 +), neodymium ions (Nd 3+), samarium ions (Sn 4+,Sn2+), europium ions (Eu 3+), Any one or more of erbium ions (Er 3+), tungsten ions (W 6+), and the initial metal ions are not the same as the replacement metal ions.
In an embodiment of the present application, the initial metal ion contained in the rigid metal-organic framework material may be an aluminum ion, and the replacement metal ion used in step S2 may be any one or more selected from iron ion, chromium ion, titanium ion, manganese ion, and vanadium ion.
In an embodiment of the present application, the initial metal ion contained in the rigid metal-organic framework material may be zirconium ion, and the replacement metal ion used in step S2 may be any one or more selected from cobalt ion, chromium ion, iron ion, titanium ion, and hafnium ion.
In an embodiment of the present application, the initial metal ion contained in the rigid metal-organic framework material may be a chromium ion, and the replacement metal ion used in step S2 may be any one or more selected from aluminum ion, iron ion, titanium ion, manganese ion, tungsten ion, and vanadium ion.
In an embodiment of the present application, the initial metal ion contained in the rigid metal-organic framework material may be one of magnesium ion, calcium ion, strontium ion, barium ion, zinc ion, copper ion, cobalt ion, iridium ion, nickel ion, cadmium ion, and the replacement metal ion used in step S2 may be one or more selected from beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, titanium ion, zirconium ion, hafnium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, cadmium ion, aluminum ion, indium ion, lanthanum ion, cerium ion, neodymium ion, samarium ion, europium ion, erbium ion, tungsten ion, and the initial metal ion is different from the replacement metal ion.
In an embodiment of the present application, the organic ligands contained in the rigid metal-organic framework material and the flexible metal-organic framework material bear a functional group that can form a coordination bond with one or more of the initial metal ions or the alternative metal ions, which can be selected from any one or more ：-COOH、-NO2、-Si(OH)3、-PO3H、-CH(RSH)2、-C(RSH)3、-CH(ROH)2、-C(ROH)3、-CH(RCN)2、-C(RCN)3, of the following functional groups wherein R can be an alkylene group having 1 to 5 carbon atoms.
In embodiments of the present application, the organic ligand contained in the rigid metal-organic framework material may have a functional group-COOH that may form a coordinate bond with one or more of the initial metal ions or the replacement metal ions.
In embodiments of the present application, the organic ligand contained in the rigid metal-organic framework material may be derived from a dicarboxylic acid, a tricarboxylic acid, or a tetracarboxylic acid.
In the description of the present application, the term "derived from" means that the organic ligand is present in the metal-organic framework material in a fully or partially deprotonated form or in a completely non-deprotonated form. For example, when the organic ligand is derived from a carboxylic acid, the carboxylic acid may be present in the metal-organic framework at least in part in the form of a carboxylate; of course, carboxylic acids may also be present in the metal-organic framework. The term "derived from" also includes substituted derivatives of organic ligands, suitable substituents may be hydroxy, methyl, ethyl, fluoro, chloro, bromo, amino (NH 2), phenyl or benzyl.
In embodiments of the present application, the organic ligand contained in the rigid metal-organic framework material may be derived from a dicarboxylic acid, for example, may be derived from oxalic acid, succinic acid, tartaric acid, 1, 4-butane dicarboxylic acid, 1, 4-butene dicarboxylic acid, 4-oxo-pyran-2, 6-dicarboxylic acid, 1, 6-hexane dicarboxylic acid, decanedicarboxylic acid, 1, 8-heptadecanedicarboxylic acid, 1, 9-heptadecanedicarboxylic acid, acetylene dicarboxylic acid, 1, 2-phthalic acid, 1, 3-phthalic acid, 2, 3-pyridine dicarboxylic acid, pyridine-2, 3-dicarboxylic acid, 1, 3-butadiene-1, 4-dicarboxylic acid (fumaric acid), 1, 4-phthalic acid, terephthalic acid, imidazole-2, 4-dicarboxylic acid, 2-methylquinoline-3, 4-dicarboxylic acid, quinoline-2, 4-dicarboxylic acid, quinoxaline-2, 3-dicarboxylic acid, 6-chloroquinoxaline-2, 3-dicarboxylic acid, 4 '-diaminophenylmethane-3, 3' -dicarboxylic acid, quinoline-3, 4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2, 8-dicarboxylic acid, diimine dicarboxylic acid, pyridine-2, 6-dicarboxylic acid, 2-methylimidazole-4, 5-dicarboxylic acid, thiophene-3, 4-dicarboxylic acid, 2-isopropylimidazole-4, 5-dicarboxylic acid, tetrahydropyran-4, 4-dicarboxylic acid, Perylene-3, 9-dicarboxylic acid, perylene dicarboxylic acid, pluriol E200-dicarboxylic acid, 3, 6-dioxaoctane dicarboxylic acid, 3, 5-cyclohexadiene-1, 2-dicarboxylic acid, octane dicarboxylic acid, pentane-3, 3-carboxylic acid, 4 '-diamino-1, 1' -biphenyl-3, 3 '-dicarboxylic acid, 4' -diaminobiphenyl-3, 3 '-dicarboxylic acid, benzidine-3, 3' -dicarboxylic acid, 1, 4-bis (phenylamino) benzene-2, 5-dicarboxylic acid, 1 '-binaphthyl dicarboxylic acid, 7-chloro-8 methylquinoline-2, 3-dicarboxylic acid, 1-anilinoanthraquinone-2, 4' -dicarboxylic acid, Polytetrahydrofuran 250-dicarboxylic acid, 1, 4-bis (carboxymethyl) piperazine-2, 3-dicarboxylic acid, 7-chloroquinoline-3, 8-dicarboxylic acid, 1- (4-carboxy) phenyl-3- (4-chloro) phenylpyrazoline-4, 5-dicarboxylic acid, 1,4,5,6, 7-hexachloro-5-norbornene-2, 3-dicarboxylic acid, phenylindane dicarboxylic acid, 1, 3-dibenzyl-2-oxoimidazolidinyl-4, 5-dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, naphthalene-1, 8-dicarboxylic acid, 2-benzoylbenzene-1, 3-dicarboxylic acid, 1, 3-dibenzyl-2-oxoimidazolidinyl-4, 5-cis-dicarboxylic acid, 2,2' -biquinoline-4, 4' -dicarboxylic acid, pyridine-3, 4-dicarboxylic acid, 3,6, 9-trioxaundecanedicarboxylic acid, hydroxybenzophenone dicarboxylic acid, pluriol E300-dicarboxylic acid, pluriol E400-dicarboxylic acid, pluriol E600-dicarboxylic acid, pyrazole-3, 4-dicarboxylic acid, 2, 3-pyrazinedicarboxylic acid, 5, 6-dimethyl-2, 3-pyrazinedicarboxylic acid, 4' -diaminodiphenyl ether diimine dicarboxylic acid, 4' -diaminodiphenylmethane diimine dicarboxylic acid, 4' -diaminodiphenyl sulfone diimine dicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 3-adamantanedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 8-methoxy-2, 3-naphthalenedicarboxylic acid, 8-nitro-2, 3-naphthalenedicarboxylic acid, 8-sulfo-2, 3-naphthalenedicarboxylic acid, anthracene-2, 3-dicarboxylic acid, 2',3' -diphenyl-p-terphenyl-4, 4 "-dicarboxylic acid, (diphenyl ether) -4,4' -dicarboxylic acid, imidazole-4, 5-dicarboxylic acid, 4 (1H) -oxo-benzothiopyran-2, 8-dicarboxylic acid, 5-tert-butyl-1, 3-phthalic acid, 7, 8-quinolinedicarboxylic acid, 4, 5-imidazole dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, tricetyl dicarboxylic acid, tetradecanedicarboxylic acid, 1, 7-heptanedicarboxylic acid, 5-hydroxy-1, 3-phthalic acid, 2, 5-dihydroxy-1, 4-phthalic acid, pyrazine-2, 3-dicarboxylic acid, furan-2, 5-dicarboxylic acid, 1-nonene-6, 9-dicarboxylic acid, eicosenedicarboxylic acid, 4 '-dihydroxydiphenylmethane-3, 3' -dicarboxylic acid, 1-amino-4-methyl-9, 10-dioxo-9, 10-dihydroanthracene-2, 3-dicarboxylic acid, 2, 5-pyridinedicarboxylic acid, cyclohexene-2, 3-dicarboxylic acid, 2, 9-dichlororubrene-4, 11-dicarboxylic acid, 7-chloro-3-methylquinoline-6, 8-dicarboxylic acid, 2, 4-dichlorobenzophenone-2 ',5' -dicarboxylic acid, 1, 3-phthalic acid, 2, 6-pyridinedicarboxylic acid, 1-methylpyrrolidine-3, 4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3, 4-dicarboxylic acid, anthraquinone-1, 5-dicarboxylic acid, 3, 5-pyrazoledicarboxylic acid, 2-nitrobenzene-1, 4-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, cyclobutane-1, 1-dicarboxylic acid, 1, 14-tetradecanedicarboxylic acid, 5, 6-dehydronorbornane-2, 3-dicarboxylic acid, 5-ethyl-2, 3-pyridinedicarboxylic acid or camphordicarboxylic acid.
In embodiments of the present application, the organic ligand contained in the rigid metal-organic framework material may be derived from a tricarboxylic acid, for example, may be derived from 2-hydroxy-1, 2, 3-propanetricarboxylic acid, 7-chloro-2, 3, 8-quinolinetricarboxylic acid, 1,2,3-,1,2, 4-benzotricarboxylic acid, 1,2, 4-butanetricarboxylic acid, 2-phosphono-1, 2, 4-butanetricarboxylic acid, 1,3, 5-benzotricarboxylic acid, 1-hydroxy-1, 2, 3-propanetricarboxylic acid, 4, 5-dihydro-4, 5-dioxo-1H-pyrrolo [2,3-F ] quinoline-2, 7, 9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1, 2, 4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1, 2, 4-tricarboxylic acid, 1,2, 3-propanetricarboxylic acid or aurin.
In embodiments of the application, the organic ligand contained in the rigid metal-organic framework material may be derived from a tetracarboxylic acid, e.g. may be derived from 1, 1-dioxoperyno [1,12-BCD ] thiophene-3, 4,9, 10-tetracarboxylic acid, perylene tetracarboxylic acids such as perylene-3, 4,9, 10-tetracarboxylic acid or (perylene-1, 12-sulfone) -3,4,9, 10-tetracarboxylic acid, butane tetracarboxylic acids such as 1,2,3, 4-butane tetracarboxylic acid or meso-1, 2,3, 4-butane tetracarboxylic acid, decane-2, 4,6, 8-tetracarboxylic acid, 1,4,7,10,13, 16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4, 5-benzene tetracarboxylic acid, 1,2,11, 12-dodecane tetracarboxylic acid, 1,2,5, 6-hexane tetracarboxylic acid, 1,2,7, 8-octane tetracarboxylic acid, 1,4,5, 8-naphthalene tetracarboxylic acid, 1,2,9,10-decane tetracarboxylic acid, benzophenone tetracarboxylic acid, 3', 4' -benzophenone tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid or cyclopentane tetracarboxylic acid such as cyclopentane-1, 2,3, 4-tetracarboxylic acid.
In embodiments of the present application, the ratio of the total moles of replacement metal ions employed in step S2 to the total moles of initial metal ions contained in the rigid metal-organic framework material may be (0.1 to 2): 1, for example, may be 0.1:1,0.2:1,0.4:1,0.6:1,0.8:1,1:1,1.2:1,1.4:1,1.6:1,1.8:1 or 2:1.
In the description of the present application, "total moles of replacement metal ions" refers to the sum of the moles of one or more replacement metal ions employed in step S2; "total moles of initial metal ions" refers to the sum of the moles of one or more initial metal ions contained in the rigid metal-organic framework material employed in step S2.
In an embodiment of the present application, in step S2, the reaction temperature at which the metal ion substitution reaction is performed may be in the range of 0 ℃ to 250 ℃, for example, the reaction temperature may be 0 ℃,20 ℃,40 ℃,60 ℃,80 ℃,100 ℃,120 ℃,140 ℃,150 ℃,160 ℃,180 ℃,200 ℃,220 ℃,235 ℃, or 250 ℃.
In the embodiment of the present application, in step S2, the reaction temperature at which the metal ion substitution reaction is performed may be maintained by means of water bath heating or oil bath heating.
In an embodiment of the present application, in step S2, the reaction time for the metal ion substitution reaction may be in the range of 2h to 96h, for example, the reaction time may be 2h,4h,8h,10h,12h,14h,16h,18h,20h,22h,24h,30h,35h,40h,44h,48h,55h,60h,65h,70h,75h,80h,85h,90h or 96h.
In an embodiment of the present application, in step S2, the reaction pressure at which the metal ion substitution reaction is performed may be in the range of 0.1bar to 20bar, for example, the reaction pressure may be 0.1bar,1bar,2b ar,4bar,6bar,8bar,10bar,12bar,14bar,16bar,18bar or 20bar.
In the embodiment of the present application, in step S2, the metal ion substitution reaction may be performed without stirring or with stirring, preferably with stirring.
In the embodiment of the present application, when the substitution reaction of the metal ions is performed under stirring conditions, the stirring speed of the stirring is not more than 1000rpm, for example, the stirring speed of the stirring may be 100rpm,200rpm,300rpm,400rpm,500rpm,600rpm,700rpm,800rpm,900rpm or 1000rpm.
In an embodiment of the present application, in step S2, the metal ion substitution reaction may be performed in the presence of a first solvent.
In the embodiment of the present application, in step S2, the metal ion substitution reaction may be a hydrothermal synthesis reaction or a solvothermal synthesis reaction, and the first solvent used in the hydrothermal synthesis reaction is water; the first solvent used in the solvothermal synthesis reaction can be water, alcohols, amide solvents, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetonitrile, toluene, chlorobenzene, methyl Ethyl Ketone (MEK), tetrahydrofuran (THF), ethyl acetate or a mixed solvent formed by mixing the solvents according to a certain proportion.
In an embodiment of the present application, the alcohol is preferably any one or more of methanol, ethanol, propanol, butanol, pentanol and hexanol.
In an embodiment of the present application, the amide-based solvent is preferably any one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) and N, N-Diethylformamide (DEF).
In an embodiment of the present application, in step S3, the flexible metal-organic framework material may be separated by suction filtration, filtration or centrifugation.
In an embodiment of the application, in step S3, after separation of the flexible metal-organic framework material,
The drying temperature at which it is dried may be in the range of 80 ℃ to 160 ℃, for example, the drying temperature may be 80 ℃,90 ℃,100 ℃,110 ℃,120 ℃,130 ℃,140 ℃,150 ℃ or 160 ℃;
The drying pressure may be in the range of 0.001atm to 1atm, for example, the drying pressure may be 0.001atm,0.005atm,0.01atm,0.05atm,0.1atm,0.5atm,1atm, where atm refers to atmospheric pressure, 1 atm=101325 pa=1.01325 bar;
The drying time may be in the range of 2 hours to 16 hours, for example, the drying time may be 2 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 14 hours or 16 hours.
In an embodiment of the present application, step S1 may include: preparing the rigid metal-organic framework material by hydrothermal synthesis or solvothermal synthesis; the specific steps may include:
Adding one or more precursors of the initial metal and an organic ligand to a second solvent, forming a rigid metal-organic framework material containing one or more initial metal ions by hydrothermal synthesis or solvothermal synthesis;
and separating the rigid metal-organic framework material containing one or more initial metal ions from the reaction liquid, and drying the reaction liquid to obtain the rigid metal-organic framework material product for later use.
In an embodiment of the present application, the reaction temperature at which the rigid metal-organic framework material is prepared by the hydrothermal synthesis method or the solvothermal synthesis method in step S1 may be in the range of 0 ℃ to 220 ℃, for example, the reaction temperature may be 0 ℃,20 ℃,40 ℃,60 ℃,80 ℃,100 ℃,120 ℃,140 ℃,150 ℃,160 ℃,180 ℃,200 ℃, or 220 ℃.
In an embodiment of the present application, the reaction time in preparing the rigid metal-organic framework material by the hydrothermal synthesis method or the solvothermal synthesis method in step S1 may be in the range of 2h to 96h, for example, the reaction time may be 2h,4h,8h,10h,12h,14h,16h,18h,20h,22h,24h,30h,35h,40h,44h,48h,55h,60h,65h,70h,75h,80h,85h,90h or 96h.
In an embodiment of the present application, the reaction pressure at which the rigid metal-organic framework material is prepared by hydrothermal synthesis or solvothermal synthesis in step S1 may be in the range of 0.1bar to 20bar, for example, the reaction pressure may be 0.1bar,1bar,2b ar,4bar,6bar,8bar,10bar,12bar,14bar,16bar,18bar or 20bar.
In an embodiment of the present application, the preparation of the rigid metal-organic framework material by the hydrothermal synthesis method or the solvothermal synthesis method in step S1 may be performed under stirring conditions, and the stirring speed of the stirring may be in the range of 50rpm to 1000 rpm.
In the embodiment of the present application, the second solvent used in the preparation of the rigid metal-organic framework material in step S1 by the hydrothermal synthesis method or the solvothermal synthesis method may be water, alcohols, amide solvents, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetonitrile, toluene, chlorobenzene, methyl Ethyl Ketone (MEK), tetrahydrofuran (THF), ethyl acetate or a mixed solvent formed by mixing them according to a certain ratio; the alcohol is preferably any one or more of methanol, ethanol, propanol, butanol, pentanol and hexanol; the amide-based solvent is preferably any one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) and N, N-Diethylformamide (DEF).
In an embodiment of the present application, in step S1, the rigid metal-organic framework material containing one or more initial metal ions may be separated from the reaction solution by suction filtration, filtration or centrifugation.
In an embodiment of the application, in step S1, after separating the rigid metal-organic framework material containing one or more initial metal ions from the reaction solution,
The drying temperature at which it is dried may be in the range of 80 ℃ to 160 ℃, for example, the drying temperature may be 80 ℃,90 ℃,100 ℃,110 ℃,120 ℃,130 ℃,140 ℃,150 ℃ or 160 ℃;
The drying pressure may be in the range of 0.001atm to 1atm, for example, the drying pressure may be 0.001atm,0.005atm,0.01atm,0.05atm,0.1atm,0.5atm,1atm;
The drying time may be in the range of 2 hours to 16 hours, for example, the drying time may be 2 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 14 hours or 16 hours.
The embodiment of the application also provides a flexible metal-organic framework material, which is obtained by the method for preparing the flexible metal-organic framework material.
In an exemplary embodiment of the present application, the flexible metal-organic framework material may contain a replacement metal ion Fe 3+, and may further contain an initial metal ion Al 3+, and an organic ligand derived from fumaric acid coordinated to the metal ion.
In an exemplary embodiment of the present application, the flexible metal-organic framework material may contain a replacement metal ion Co 2+, and may further contain an initial metal ion Zr 4+, and a fumaric-derived organic ligand coordinated to the metal ion.
In an exemplary embodiment of the present application, the flexible metal-organic framework material may contain a replacement metal ion Ti 4+, and may also contain an initial metal ion Cr 3+, and an organic ligand derived from terephthalic acid coordinated to the metal ion.
In an exemplary embodiment of the present application, the flexible metal-organic framework material may contain a replacement metal ion Cu 2+, and may further contain an initial metal ion Mg 2+, and an organic ligand derived from fumaric acid coordinated to the metal ion.
In an exemplary embodiment of the present application, the flexible metal-organic framework material may contain a replacement metal ion Zn 2+, and may further contain an initial metal ion Sr 2+, and an organic ligand derived from fumaric acid coordinated to the metal ion.
The flexible metal-organic framework material provided by the embodiment of the application has the following advantages:
1. The preparation process of the flexible metal-organic framework material provided by the embodiment of the application does not need to adopt flexible at least bidentate organic ligands, does not involve the functional modification of the organic ligands participating in the formation of the metal-organic framework material, and can be prepared by only carrying out one-step metal ion replacement reaction after the metal-organic framework material with a rigid structure is obtained, and the preparation method has the advantages of simple process and low production cost; in addition, the preparation process does not need to use a plurality of organic synthesis equipment, so that the production cost of the flexible metal-organic framework material can be further reduced;
2. The preparation process of the flexible metal-organic framework material provided by the embodiment of the application does not involve functional modification of the metal-organic framework material under the severe reaction condition, and can avoid structural collapse of the metal-organic framework material under the severe reaction condition;
3. The flexible metal-organic framework material provided by the embodiment of the application does not belong to metal-organic framework materials with two-dimensional stacked structures or three-dimensional pore interpenetrating structures, and the occurrence of unexpected situations that the prepared metal-organic framework material cannot show the two-dimensional stacked structures or the three-dimensional pore interpenetrating structures can be avoided;
4. The performance of the flexible metal-organic framework material provided by the embodiment of the application can be predicted at the beginning of synthesis; the adsorption material has good adsorption performance, and can contain more guest molecules due to structural deformation in the process of adsorbing the guest molecules;
therefore, the flexible metal-organic framework material provided by the embodiment of the application is suitable for industrial mass production.
Examples: preparation of metal-organic framework materials with flexible structures
Example 1
S1: synthesis of rigid metal-organic framework materials
Putting 25mmol of aluminum sulfate octadeca hydrate (Al 2(SO4)3·18H2 O) and 25mmol of fumaric acid (C 4H4O4) into 60ml of water, reacting for 8 hours at the temperature of 120 ℃ under the pressure of about 2.0bar under the stirring condition (the stirring speed is 50 rpm), separating a product from mother liquor by a suction filtration mode after the reaction is finished, and completely drying at the temperature of 100 ℃, wherein the obtained product is MOF 1-rigidity;
S2: metal ion substitution
Taking 5g of the product obtained after drying in the step S1, adding into 40ml of ethanol (C 2H5 OH), adding 16mmol of ferric trichloride hexahydrate (FeCl 3·6H2 O) (the mole ratio of Fe in the ferric trichloride hexahydrate to Al 3+ to be replaced in the metal-organic framework material MOF 1-rigidity of a rigid structure is 0.5:1), and carrying out hydrothermal synthesis reaction on the mixed solution for 8h under the conditions of temperature 120 ℃ and pressure of about 2.0bar and stirring (the stirring speed is 50 rpm) to finish the reaction;
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the obtained solid crystals are separated from the mother solution by a suction filtration mode and are completely dried at 100 ℃ to obtain a dried flexible metal-organic framework material, which is recorded as MOF1.
Example 2
S1: synthesis of rigid metal-organic framework materials
15Mmol of zirconium oxychloride octahydrate (ZrOCl 2·8H2 O) and 30mmol of fumaric acid (C 4H4O4) are put into 60ml of water to react for 24 hours under the conditions of the temperature of 120 ℃ and the pressure of about 2.0bar and stirring (the stirring speed is 50 rpm), after the reaction is finished, the product is separated from the mother liquor by a suction filtration mode, and the mother liquor is completely dried at the temperature of 100 ℃, and the obtained product is marked as MOF 2-rigidity;
S2: metal ion substitution
Taking 2g of the product obtained after drying in the step S1, adding 50ml of water, adding 1.6g of cobalt nitrate (Co (NO 3)2) (the mole ratio of Co in the cobalt nitrate to Zr 4+ to be replaced in the MOF 2-rigidity of the metal-organic framework material with a rigid structure is 1:1), and carrying out hydrothermal synthesis reaction on the mixed solution for 24h at the temperature of 80 ℃ under normal pressure (about 1 bar) and under stirring conditions (the stirring speed is 500 rpm), so that the reaction is finished;
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the obtained solid crystals are separated from the mother solution by a suction filtration mode and are completely dried at 100 ℃ to obtain a dried flexible metal-organic framework material, which is recorded as MOF2.
Example 3
S1: synthesis of rigid metal-organic framework materials
Putting 25mmol of chromium nitrate nonahydrate (Cr (NO 3)3·9H2 O) and 25mmol of terephthalic acid (C 8H6O4) into 50ml of water, performing hydrothermal synthesis reaction for 16 hours at 180 ℃ and under the pressure of about 10.2bar (without stirring), separating a product from mother liquor by a suction filtration mode after the reaction is finished, and completely drying at 120 ℃ to obtain a product which is marked as MOF 3-rigidity;
S2: metal ion substitution
Taking 2g of the product obtained after drying in the step S1, adding 100ml of water, adding 17.6mmol of titanium tetrachloride (TiCl 4) (the molar ratio of Ti in the titanium tetrachloride to Cr 3+ to be replaced in the MOF 3-rigidity of the metal-organic framework material with a rigid structure is 2:1) into the water, carrying out hydrothermal synthesis reaction for 10h at the temperature of 120 ℃ under the pressure of about 2.0bar under the stirring condition (the stirring speed is 50 rpm), and finishing the reaction;
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the obtained solid crystals are separated from the mother solution by a suction filtration mode and are completely dried at 100 ℃ to obtain a dried flexible metal-organic framework material, which is recorded as MOF3.
Example 4
S1: synthesis of rigid metal-organic framework materials
10Mmol of magnesium nitrate hexahydrate (Mg (NO 3)2·6H2 O) and 10mmol of tetra [4- (carboxyphenyl) methoxy ] methane (C 33H24O12) are put into a mixed solution prepared by 90ml of dimethylacetamide (DMAc) and 10ml of water, the hydrothermal synthesis reaction is carried out for 48 hours under the conditions of the temperature of 150 ℃ and the pressure of about 4.8bar (without stirring), after the reaction is finished, the product is separated from the mother solution by a suction filtration mode, the product is washed by fresh pure dimethylacetamide for 3 times at normal temperature (20 ml of DMAc is used each time), and the washed product is completely dried at the temperature of 150 ℃, so that the obtained product is marked as MOF 4-rigidity;
S2: metal ion substitution
Taking 1g of the product obtained after drying in the step S1, putting 50ml of dimethylacetamide, putting 4.6mmol of copper sulfate (CuSO 4) into the dimethylacetamide (the molar ratio of Cu in the copper sulfate to Mg 2+ to be replaced in the MOF 4-rigidity of the metal-organic framework material with a rigid structure is 0.8:1), and carrying out hydrothermal synthesis reaction for 24 hours at the temperature of 120 ℃ under the pressure of about 2.0bar under the stirring condition (the stirring speed is 50 rpm) to finish the reaction;
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the obtained solid crystals are separated from the mother solution by a suction filtration mode and are completely dried at 150 ℃ to obtain a dried flexible metal-organic framework material, which is recorded as MOF4.
Example 5
S1: synthesis of rigid metal-organic framework materials
10Mmol of strontium nitrate (Sr (NO 3)2) and 10mmol of tetra [4- (carboxyphenyl) methoxy ] methane (C 33H24O12) are put into 100ml of N, N-Dimethylformamide (DMF), hydrothermal synthesis reaction is carried out for 48 hours under the conditions of the temperature of 150 ℃ and the pressure of about 4.8bar (without stirring), after the reaction is finished, the product is separated from mother liquor by a suction filtration mode, the product is washed for 3 times at normal temperature by using fresh pure N, N-dimethylformamide (20 ml of DMF is used each time), and the washed product is completely dried at the temperature of 150 ℃, and the obtained product is marked as MOF 5-rigidity;
Among them, tetrakis [4- (carboxyphenyl) methoxy ] methane (C 33H24O12) was prepared by the method disclosed in reference Hideaki Oike et al.Tailored Synthesis of Branched and Network Polymer Structures by Electrostatic Self-Assembly and Covalent Fixation with Telechelic Poly(THF)Having N-Phenylpyrrolidinium Salt Groups,Macromolecules 1999,32,4819-4825 (see page 4820 (b) Tetracarboxylic Acid (4). Part).
S2: metal ion substitution
Putting 1g of the product obtained after drying in the step S1 into 50ml of N, N-dimethylformamide, adding 2mmol of zinc nitrate hexahydrate (Zn (NO 3)2·6H2 O) (the mole ratio of Zn in the zinc nitrate hexahydrate to Sr 2+ to be replaced in the metal-organic framework material MOF 5-rigidity of a rigid structure is 2:1), and carrying out hydrothermal synthesis reaction for 24 hours under the conditions of temperature 130 ℃ and pressure of about 2.7bar and stirring (the stirring speed is 50 rpm);
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the obtained solid crystals are separated from the mother solution by suction filtration, and are completely dried at 150 ℃ to obtain a dried flexible metal-organic framework material, which is recorded as MOF5.
Comparative example
Comparative examples 1 to 3 the subsequent steps were carried out on the basis of the metal-organic framework materials of the rigid structures obtained in step S1 of examples 1 to 3, respectively.
Comparative example 1
S2: metal ion replacement;
Taking 5g of the product obtained after drying in the step S1 of example 1, putting into 40ml of ethanol (C 2H5 OH), putting 16mmol of copper sulfate (CuSO 4) into the ethanol (the molar ratio of Cu in the copper sulfate to Al 3+ to be replaced in the MOF 1-rigid metal-organic framework material with a rigid structure is 0.5:1), and carrying out hydrothermal synthesis reaction on the mixed solution for 8h under the conditions of temperature 120 ℃ and pressure of about 2.0bar and stirring (the stirring speed is 50 rpm) to finish the reaction;
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the obtained solid crystals are separated from the mother solution by suction filtration, and are completely dried at 100 ℃.
The solid product was completely white and the filtered mother liquor was completely blue, indicating that the metal ions failed to be replaced.
Comparative example 2
S2: metal ion replacement;
Taking 2g of the product obtained after drying in the step S1 of the example 2, putting into 50ml of DMF, putting 8.8mmol of ferric chloride hexahydrate (FeCl 3·6H2 O) into the DMF (the mole ratio of Fe in the ferric chloride hexahydrate to Zr 4+ to be replaced in the MOF 2-rigidity of the metal-organic framework material with a rigid structure is 1:1), and carrying out hydrothermal synthesis reaction on the mixed solution for 24 hours at the temperature of 150 ℃ and the pressure of about 4.8bar, and ending the reaction;
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the materials in the reaction vessel are observed to be in a cotton-like shape, which indicates that the original rigid metal-organic framework collapses in the reaction process, and Fe ions cannot coordinate with the initial organic ligand.
Comparative example 3
S2: metal ion replacement;
Taking 2g of the product obtained after drying in the step S1 of the example 3, putting 100ml of water, putting 17.6mmol of vanadium sulfate hexahydrate (VSO 4·6H2 O) into the water (the mole ratio of V in the vanadium sulfate hexahydrate to Cr 3+ to be replaced in the MOF 3-rigidity of the metal-organic framework material with a rigid structure is 2:1), and carrying out hydrothermal synthesis reaction for 8h under the conditions of 120 ℃ and about 2.0bar of pressure and stirring (the stirring speed is 50 rpm) to finish the reaction;
S3: separation of flexible metal-organic framework materials
After the temperature of the reaction solution in the step S2 is reduced to room temperature, the material in the reaction container is observed to be gelatinous, which indicates that the original rigid metal-organic framework collapses in the reaction process, and the V ions cannot coordinate with the initial organic ligand.
Comparative example 4
25Mmol of aluminum sulfate octadeca-hydrate (Al 2(SO4)3·18H2 O), 25mmol of ferric chloride hexahydrate (FeCl 3·6H2 O) and 50mmol of fumaric acid (C 4H4O4) are put into 60ml of water and reacted for 8 hours at a temperature of 120 ℃ under a pressure of about 2.0bar and under stirring conditions (stirring speed of 50 rpm), after the reaction is completed, the product is separated from the mother liquor by suction filtration and is completely dried at 100 ℃.
The observation shows that the materials in the reactor are completely white, the filtered mother liquor is reddish brown, and the product is proved to be mainly MOF 1-rigid, which indicates that the metal-organic framework MOF1 which has a flexible structure and contains metal ions of Al 3 + and Fe 3+ can not be obtained by simultaneously adding Al 3+ and Fe 3+ to coordinate with fumaric acid.
Test example: performance testing of metal-organic framework materials with flexible structures
Test example 1: flexible structural verification of metal-organic framework materials
The flexible structure of the metal-organic framework material prepared in the above examples was verified by powder X-ray diffraction (powder XRD) patterns. When the metal-organic framework material with the flexible structure is subjected to external stimulus (such as adsorption of external guest gas/liquid molecules), the structure of the metal-organic framework material is correspondingly changed, and the XRD pattern shows that the XRD characteristic peak of the material is shifted to a certain extent. In addition, this structural change is reversible and reflected in the XRD pattern shows a shift in the XRD characteristic peaks under external stimulus, which return to the original position after removal of the external stimulus.
The test adopts water molecule adsorption as external stimulus, and the structural change of the material before and after water adsorption is tested to verify that the material is in a flexible structure. MOF 1-stiffness, MOF1, MOF 2-stiffness, MOF2, MOF 3-stiffness and MOF3 materials were dry pre-treated at 110℃for 6 hours before each water adsorption test was performed.
FIG. 1 is a powder XRD pattern of MOF 1-stiffness prepared in example 1 of the present application before and after the first water absorption;
FIG. 2 is a powder XRD pattern of MOF1 prepared in example 1 of the present application before and after the first water absorption; FIG. 3 is a powder XRD pattern of MOF1 prepared in example 1 of the present application before and after the first water absorption and before and after the second water absorption; FIG. 4 is a powder XRD pattern of MOF 2-stiffness prepared in example 2 of the present application, before and after the first water absorption; FIG. 5 is a powder XRD pattern of MOF2 prepared in example 2 of the present application before and after the first water absorption; FIG. 6 is a powder XRD pattern of MOF2 prepared in example 2 of the present application before and after the first water absorption and before and after the second water absorption; FIG. 7 is a powder XRD pattern of MOF 3-stiffness prepared in example 3 of the present application, before and after the first water absorption; fig. 8 is a powder XRD pattern of MOF3 prepared in example 3 of the present application before and after the first water absorption. The X-ray powder diffractometer was Japan (Rigaku), the scanning range was 5 to 50 degrees, and the scanning speed was 5 degrees/min.
As can be seen from the XRD patterns of fig. 1 to 8:
(1) MOF 1-rigidity, MOF 2-rigidity and MOF 3-rigidity have no shift of characteristic peaks before and after the first water absorption;
(2) Compared with the XRD pattern before the first water absorption, the characteristic peaks of the MOF1, the MOF2 and the MOF3 are wholly shifted leftwards after the first water absorption; the characteristic peaks of MOF1 and MOF2 after secondary water absorption are wholly offset leftwards compared with the XRD pattern before secondary water absorption;
According to bragg equation 2dsin θ=nλ, it can be obtained that when the diffraction angle θ is reduced, the interplanar spacing d is increased, which indicates that after the MOF1 and MOF2 materials absorb external water molecules, the whole structure of the MOF1 and MOF2 materials is expanded, and proves that the metal-organic framework materials with flexible structures are truly obtained through metal ion substitution reaction in examples 1 and 2;
(note: in bragg equation 2dsin θ=nλ, d represents the interplanar spacing, θ represents the angle between the incident X-ray and the corresponding crystal plane, λ is the wavelength of the X-ray, n is the diffraction order; nλ is a constant in the same test);
(2) The structural changes of MOF1 and MOF2 are reversible: after the first water absorption, the characteristic peaks of the MOF1 and MOF2 materials are offset leftwards, after the first water absorption test is finished and before the second water absorption test is carried out, the characteristic peaks of the MOF1 and MOF2 materials are offset rightwards relative to the first water absorption and return to the original positions after being dried for 6 hours, and the flexible structures of the MOF1 and MOF2 materials can be reversibly changed under the external stimulus after metal ion replacement.
Test example 2: adsorption performance verification of metal-organic framework material
The test example verifies the adsorption performance of the metal-organic framework material prepared by the embodiment of the application through a water vapor adsorption performance test. Before testing, the metal-organic framework material prepared by the embodiment of the application is dried for 6 hours under the conditions of the temperature of 110 ℃ and the pressure of 0.1atm, so as to carry out drying, and then the water vapor adsorption curve, namely the variation curve of the water vapor adsorption capacity (wt.%) along with the relative pressure P/P 0 is tested, wherein,
P refers to the steam pressure at any moment in the test process, P 0 refers to the saturated steam pressure at a certain temperature (298K in the test example, the saturated steam pressure is P 0 = 3.169 kPa), the test is carried out in a closed environment, the real-time humidity is P, and the environment humidity is irrelevant to the test (the environment humidity is 65%RH); the manufacturer of the water vapor adsorption instrument is Michael, and the model is BELSORP-max.
FIG. 9 is a graph showing the rigidity of MOF 1-and the water vapor adsorption curve of MOF1 obtained in example 1 of the present application; FIG. 10 is a graph showing the rigidity of MOF2 and the water vapor adsorption curve of MOF2 obtained in example 2 of the present application; FIG. 11 is a graph showing the rigidity of MOF3 and the water vapor adsorption curve of MOF3 obtained in example 3 of the present application.
As can be seen from fig. 9 to 11:
Compared with metal ion-replaced raw materials, namely metal-organic framework materials MOF 1-rigidity, MOF 2-rigidity and MOF 3-rigidity with rigid structures, after metal ion replacement, the adsorption quantity of the MOF1, MOF2 and MOF3 materials to water vapor is increased, which means that the water adsorption performance of the MOF1, MOF2 and MOF3 materials is improved relative to the corresponding rigid metal-organic framework materials, and the metal ion replacement can convert the rigid structure of the metal-organic framework materials into a flexible structure, so that the performance of the metal-organic framework materials is improved.
In addition, the end products obtained in examples 4 and 5 have certain flexibility characteristics compared with the corresponding MOF 4-rigidity and MOF 5-rigidity, and the crystal structures of the end products can be expanded to a certain extent after water absorption.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the application, and all equivalent structural changes made by the specification and drawings of the present application or direct/indirect application in other related technical fields are included in the scope of the present application.
Claims (11)
1. A method for preparing a flexible metal-organic framework material, comprising:
S1: providing a rigid metal-organic framework material; wherein the rigid metal-organic framework material is formed from at least one initial metal ion and an organic ligand coordinated to the initial metal ion;
S2: replacing at least one initial metal ion in the rigid metal-organic framework material with at least one replacement metal ion, and performing metal ion replacement reaction on the rigid metal-organic framework material to obtain a flexible metal-organic framework material;
Wherein the flexible metal-organic framework material comprises a replacement metal ion and an organic ligand coordinated to the replacement metal ion;
When the initial metal ion is Al 3+, the replacement metal ion is Fe 3+;
When the initial metal ion is Zr 4+, the replacement metal ion is Co 2+;
When the initial metal ion is Cr 3+, the replacement metal ion is Ti 4 +;
when the initial metal ion is Mg 2+, the replacement metal ion is Cu 2+;
when the initial metal ion is Sr 2+, the replacement metal ion is Zn 2+.
2. The method of making according to claim 1, wherein the flexible metal-organic framework material further comprises an initial metal ion and an organic ligand coordinated to the initial metal ion.
3. The method of claim 1, wherein the metal ion substitution reaction is a hydrothermal synthesis reaction or a solvothermal synthesis reaction.
4. The method of manufacturing as set forth in claim 1, further comprising: after the step S2 of the process, the process proceeds,
S3: and (2) separating the flexible metal-organic framework material from the reaction liquid containing the flexible metal-organic framework material obtained in the step (S2), and drying to obtain a flexible metal-organic framework material product.
5. The method according to any one of claims 1 to 4, wherein in step S2, the ratio of the total moles of the replacement metal ions to the total moles of the initial metal ions contained in the rigid metal-organic framework material is (0.1 to 2): 1.
6. The production method according to any one of claims 1 to 4, wherein the reaction temperature of the metal ion substitution reaction is 0 ℃ to 250 ℃.
7. The method according to any one of claims 1 to 4, wherein the reaction time of the metal ion substitution reaction is 2 to 96 hours.
8. The method according to any one of claims 1 to 4, wherein the reaction pressure of the metal ion substitution reaction is 0.1 bar to 20 bar.
9. The method according to any one of claims 1 to 4, wherein the metal ion substitution reaction is carried out under stirring conditions at a stirring speed of not more than 1000 rpm.
10. The method according to claim 3, wherein the metal ion substitution reaction is carried out in the presence of a solvent selected from one or more of water, methanol, ethanol, propanol, butanol, pentanol, hexanol, dimethylformamide, dimethylacetamide, diethylformamide, dimethylsulfoxide, N-methylpyrrolidone, acetonitrile, toluene, chlorobenzene, methylethylketone, tetrahydrofuran, and ethyl acetate.
11. A flexible metal-organic framework material obtained by the preparation method according to any one of claims 1 to 10.
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