CN105536574B - Filter membrane and its preparation method and application - Google Patents
Filter membrane and its preparation method and application Download PDFInfo
- Publication number
- CN105536574B CN105536574B CN201510934863.0A CN201510934863A CN105536574B CN 105536574 B CN105536574 B CN 105536574B CN 201510934863 A CN201510934863 A CN 201510934863A CN 105536574 B CN105536574 B CN 105536574B
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- Prior art keywords
- metal
- filter membrane
- polymer
- organic framework
- framework materials
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000463 material Substances 0.000 claims abstract description 111
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 86
- 229920000642 polymer Polymers 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000009987 spinning Methods 0.000 claims abstract description 52
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims description 70
- 239000002184 metal Substances 0.000 claims description 60
- 239000013110 organic ligand Substances 0.000 claims description 44
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 21
- -1 polytetrafluoroethylene Polymers 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004793 Polystyrene Substances 0.000 claims description 15
- 229920002223 polystyrene Polymers 0.000 claims description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 13
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 229920005594 polymer fiber Polymers 0.000 claims description 12
- 239000002121 nanofiber Substances 0.000 claims description 11
- 239000013384 organic framework Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229910006069 SO3H Inorganic materials 0.000 claims description 5
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229910052789 astatine Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229920001596 poly (chlorostyrenes) Polymers 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 238000003618 dip coating Methods 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 29
- 238000012360 testing method Methods 0.000 description 24
- 238000000634 powder X-ray diffraction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 239000004745 nonwoven fabric Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 description 2
- DVNYTAVYBRSTGK-UHFFFAOYSA-N 5-aminoimidazole-4-carboxamide Chemical compound NC(=O)C=1N=CNC=1N DVNYTAVYBRSTGK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010013975 Dyspnoeas Diseases 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
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- 150000002460 imidazoles Chemical class 0.000 description 2
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- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical class NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- URJFKQPLLWGDEI-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=[C]N1CC1=CC=CC=C1 URJFKQPLLWGDEI-UHFFFAOYSA-N 0.000 description 1
- MWZDIEIXRBWPLG-UHFFFAOYSA-N 1-methyl-1,2,4-triazole Chemical class CN1C=NC=N1 MWZDIEIXRBWPLG-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 description 1
- OMAFFHIGWTVZOH-UHFFFAOYSA-N 1-methyltetrazole Chemical class CN1C=NN=N1 OMAFFHIGWTVZOH-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- QMQZIXCNLUPEIN-UHFFFAOYSA-N 1h-imidazole-2-carbonitrile Chemical compound N#CC1=NC=CN1 QMQZIXCNLUPEIN-UHFFFAOYSA-N 0.000 description 1
- XGDRLCRGKUCBQL-UHFFFAOYSA-N 1h-imidazole-4,5-dicarbonitrile Chemical compound N#CC=1N=CNC=1C#N XGDRLCRGKUCBQL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- JVSMPWHQUPKRNV-UHFFFAOYSA-N 2h-tetrazol-5-amine;hydrate Chemical compound O.NC=1N=NNN=1 JVSMPWHQUPKRNV-UHFFFAOYSA-N 0.000 description 1
- AEZBIGVULSBTBA-UHFFFAOYSA-N 3-amino-4-(2-amino-4-carboxyphenyl)benzoic acid Chemical class NC1=CC(C(O)=O)=CC=C1C1=CC=C(C(O)=O)C=C1N AEZBIGVULSBTBA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- COYPLDIXZODDDL-UHFFFAOYSA-N 3h-benzimidazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2N=CNC2=C1 COYPLDIXZODDDL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HRGSKQRXBGCEAZ-UHFFFAOYSA-N 4-(4-carboxy-2-nitrophenyl)-3-nitrobenzoic acid Chemical class [O-][N+](=O)C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1[N+]([O-])=O HRGSKQRXBGCEAZ-UHFFFAOYSA-N 0.000 description 1
- LJUQGASMPRMWIW-UHFFFAOYSA-N 5,6-dimethylbenzimidazole Chemical compound C1=C(C)C(C)=CC2=C1NC=N2 LJUQGASMPRMWIW-UHFFFAOYSA-N 0.000 description 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 1
- KUEFXPHXHHANKS-UHFFFAOYSA-N 5-nitro-1h-1,2,4-triazole Chemical compound [O-][N+](=O)C1=NC=NN1 KUEFXPHXHHANKS-UHFFFAOYSA-N 0.000 description 1
- VYDWQPKRHOGLPA-UHFFFAOYSA-N 5-nitroimidazole Chemical compound [O-][N+](=O)C1=CN=CN1 VYDWQPKRHOGLPA-UHFFFAOYSA-N 0.000 description 1
- NBDAHKQJXVLAID-UHFFFAOYSA-N 5-nitroisophthalic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC([N+]([O-])=O)=C1 NBDAHKQJXVLAID-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
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- 238000005352 clarification Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- OPKBTADLGAZTRW-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ylmethanol Chemical compound OCC1CC=CC=C1 OPKBTADLGAZTRW-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
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- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 1
- BDTOTMBOHYUNSQ-UHFFFAOYSA-N triazole-1-carboxylic acid Chemical compound OC(=O)N1C=CN=N1 BDTOTMBOHYUNSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
-
- 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
- B01D53/22—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 diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The present invention relates to a kind of filter membranes formed by metal-organic framework materials and polymer.The present invention also provides a kind of methods of filter membrane for preparing and being formed by metal-organic framework materials and polymer, this method comprises: metal-organic framework materials and polymer contact are formed filter membrane by spinning or dip-coating.The invention further relates to filter membrane of the present invention filter out PM2.5, the purposes in volatile organic compounds.Filter membrane of the invention has many advantages, such as that specific surface area is high, surface functional group is abundant, high porosity and light transmission, ventilative, and can efficiently filter out to PM2.5 and volatile organic compounds realization.
Description
Technical field
The present invention relates to applied chemistry fields, and in particular, to one kind is formed by metal-organic framework materials and polymer
Filter membrane, prepare the method for the filter membrane, the filter membrane is filtering out the use in PM2.5 and volatile organic compounds
On the way.
Background technique
Metal organic framework is a polyporous materials, is made by metal cluster, metal oxide or metal salt and organic ligand
With one-dimensional, two-dimentional or three-dimensional reticulated channel structure is formed, there is porosity height, functional group to enrich, duct is orderly, various structures
Equal many merits, gas storage with separate, be catalyzed, the fields such as film, sensing, biomedical imaging play an important role.
In recent years, environmental problem is on the rise, high risks are brought to social development, people's lives, ecological safety, by
It is organic to the great attention of government and the volatility such as the extensive concern of broad masses of the people, especially PM2.5 and benzene homologues, formaldehyde
Compound.PM2.5 can be detained for a long time in the environment, and be extremely easy to enter human body, pacify to the health of people, life
Very big threat is brought entirely；Volatile organic contaminant is then main " arch-criminal " for causing environmental pollution, damaging human health,
It participates in atmospheric photochemical reaction, and directly results in the formation of PM2.5 in atmosphere；Volatile organic compounds is also to people's
Health has very detrimental effect, can it is carcinogenic, poison central nervous system, cause air hunger, cause expiratory dyspnea very
To death etc..Therefore there is an urgent need to find a kind of new material, method rapidly and efficiently to filter out it.
Currently, can either not be used to remove PM2.5 again the method that can be used in removing volatile organic compounds, all
It needs individually to be handled using different materials.For example, being conventionally used to filter out the material of PM2.5, including sell currently on the market
Can filter out the HEPA filter screen used in the air purifier of PM2.5, mainly be meltblown fibers, glass fibre and spinning
Viscous fiber.In addition, removing PM2.5 also by electrostatic precipitator technology.And for the aspect that filters out of volatile organic compounds, mesh
The preceding technical method and material that not can be widely applied in life.In the industrial production to volatile organic compounds
It filters out, currently used method has absorption method, absorption process, combustion method, condensation method, biological treatment etc..
Summary of the invention
The present invention provides a kind of filter membranes, are formed by metal-organic framework materials and polymer, the organic bone of metal
Frame material forms the metal organic framework part in the filter membrane, and the polymer forms the polymer fiber in the filter membrane
Part, wherein the metal-organic framework materials are acted on organic ligand by source metal and being formed.
Wherein, the source metal includes at least one of metal cluster, metal salt or metal oxide.
Preferably, the metallic element in the source metal include Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al,
At least one of Ge.
It is furthermore preferred that the metallic element includes at least one of Zn, Zr, Cu or Mg.
In filter membrane of the present invention, the organic ligand is、、、、、、OrOne of, or comprising following
Co-ordinating functionality :-CO2H、-NO2、-OH、-NH2、-CN、-SO3H、-SH、 CH(RSH)2、-C(RSH)3、-CH(RNH2)2、-C
(RNH2)3、-CH(ROH)2、-C(ROH)3、-CH(RCN)2、-C(RCN)3、-CH(NH2)2、-C(NH2)3、-CH(CN)2Or-C
(CN)3At least one of, wherein the R in co-ordinating functionality is independently represented each other the alkylene comprising 1 to 5 phenyl ring.
Preferably, the organic ligand isOr include-CO2H、-NH2Or at least one of-OH is coordinated function
The organic ligand of group.
In filter membrane of the present invention, the polymer includes polytetrafluoroethylene (PTFE), polystyrene, polyvinyl chloride, poly- second
Enol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, polymethyl acrylate, polyethylene glycol, at least one in polycarbonate
Kind.
Preferably, the polymer is polyacrylonitrile, polystyrene or polyvinylpyrrolidone.
As a kind of preferred embodiment of the invention, metal-organic framework materials described in filter membrane of the invention
Source metal is zirconium chloride, organic ligand is 2- amino terephthalic acid (TPA), and the polymer is polyacrylonitrile.
As a kind of preferred embodiment of the invention, metal-organic framework materials described in filter membrane of the invention
Source metal is copper acetate, organic ligand is trimesic acid, and the polymer is polystyrene.
As a kind of preferred embodiment of the invention, metal-organic framework materials described in filter membrane of the invention
Source metal is zinc nitrate, organic ligand is 2-methylimidazole, and the polymer is polyacrylonitrile.
As a kind of preferred embodiment of the invention, metal-organic framework materials described in filter membrane of the invention
Source metal is magnesium nitrate, organic ligand is 2,5-Dihydroxyterephthalic acid, and the polymer is polyvinylpyrrolidone.
Filter membrane of the present invention, wherein relative to 1 gram of the metal-organic framework materials, the polymer
Dosage is 0.1-10 grams.
The present invention also provides a kind of methods for preparing above-mentioned filter membrane, this method comprises: by metal-organic framework materials
With polymer contact, the metal-organic framework materials form the metal organic framework part in the filter membrane, the polymerization
Object forms the polymer fiber part in the filter membrane, wherein the metal-organic framework materials are made by source metal and organic ligand
With formation.
Wherein, the source metal includes at least one of metal cluster, metal salt or metal oxide.
Preferably, the metallic element in the source metal include Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al,
At least one of Ge.
The metallic element includes at least one of Zn, Zr, Cu or Mg.
In method of the present invention, the organic ligand is、、、、、、OrOne of, or comprising following
Co-ordinating functionality :-CO2H、-NO2、-OH、-NH2、-CN、-SO3H、-SH、-CH(RSH)2、-C(RSH)3、-CH(RNH2)2、-C
(RNH2)3、-CH(ROH)2、-C(ROH)3、-CH(RCN)2、-C(RCN)3、-CH(NH2)2、-C(NH2)3、-CH(CN)2Or-C
(CN)3At least one of, wherein the R in co-ordinating functionality is independently represented each other the alkylene comprising 1 to 5 phenyl ring.
Preferably, the organic ligand isOr include-CO2H、-NH2Or at least one of-OH co-ordinating functionality
Organic ligand.
In method of the present invention, the polymer includes polytetrafluoroethylene (PTFE), polystyrene, polyvinyl chloride, polyethylene
At least one of alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, polymethyl acrylate, polyethylene glycol, polycarbonate.
Preferably, the polymer is polyacrylonitrile, polystyrene or polyvinylpyrrolidone.
As a kind of preferred embodiment of the invention, the gold of metal-organic framework materials described in method of the invention
Category source is zirconium chloride, organic ligand is 2- amino terephthalic acid (TPA), and the polymer is polyacrylonitrile.
As a kind of preferred embodiment of the invention, the gold of metal-organic framework materials described in method of the invention
Category source is copper acetate, organic ligand is trimesic acid, and the polymer is polystyrene.
As a kind of preferred embodiment of the invention, the gold of metal-organic framework materials described in method of the invention
Category source is zinc nitrate, organic ligand is 2-methylimidazole, and the polymer is polyacrylonitrile.
As a kind of preferred embodiment of the invention, metal-organic framework materials described in filter membrane of the invention
Source metal is magnesium nitrate, organic ligand is 2,5-Dihydroxyterephthalic acid, and the polymer is polyvinylpyrrolidone.
In method of the present invention, relative to 1 gram of the metal-organic framework materials, the dosage of the polymer
It is 0.1-10 grams.
Method of the present invention, contact of the metal-organic framework materials with polymer carry out in a solvent, and opposite 1
Gram metal-organic framework materials, the dosage of solvent is 10-100 milliliters, prepares the filtering by spinning or dip-coating method
Film.
Preferably, the solvent includes water, methanol, ethyl alcohol, dimethylformamide, dimethyl acetamide, diethyl formyl
At least one of amine.
The present invention also provides filter membranes of the present invention to filter out the purposes in PM2.5.
The present invention also provides institute's filter membranes of the present invention to filter out the purposes in volatile organic compounds.
Filtering membrane filtration characteristic of the invention is very outstanding, can rapidly and efficiently filter out PM2.5 and volatile organic compound
Object, rejection rate can reach 80 % or more within 30 minutes.
Filtering film raw material of the present invention is simple and easy to get, non-hazardous property；Preparation process is easy quickly, and 10 minutes or so
Product is obtained, can be realized industrialization production；PM2.5 and volatile organic compounds can be filtered out simultaneously, and are all had efficient
Filter out efficiency, rejection rate can achieve 80% or more within 30 minutes；The filter membrane purity is high, light transmission, ventilative, ultralow vapour lock；Institute
Filter membrane is stated with certain flexibility and machinability, can be used for the preparation of a variety of protective materials；The specific surface area height of filter membrane,
Surface functional group is abundant, porosity is high, has effectively promoted and has filtered out to PM2.5 and volatile organic compounds.
PM2.5 can either not filtered out efficiently again in the prior art can efficiently filter out the material of volatile organic compounds
Material, requires individually to be filtered out using different materials.
It is conventionally used to filter out the material of PM2.5, including the air purifier that can filter out PM2.5 sold currently on the market
In the HEPA filter screen used, mainly be meltblown fibers, glass fibre and spun-bonded fibre, these materials are by micron order fiber
Composition, fibre diameter is larger, and filter effect is low, meanwhile, filtration result is by the van der Waals between PM2.5 and fibrous material
What effect was realized, it is widely different to the particulate matter filtration result of different-diameter, it has seriously affected on the whole and effect is filtered out to PM2.5
Fruit.
And for the aspect that filters out of volatile organic compounds, it not can be widely applied for the technology in life at present
Method and material.Volatile organic compounds is filtered out in the industrial production, currently used method has absorption method, absorbs
Method, combustion method, condensation method, biological treatment etc., but all there is respective deficiency, complex process, vapour lock again for these methods
Greatly, technology energy consumption is excessively high, operation cost is high, filters out low efficiency etc..
Filter membrane of the present invention can filter out PM2.5 and volatile organic compounds simultaneously, rich by filter membrane surface
Rich functional group acts on pollutant, may be implemented to filter out different-grain diameter, the efficient of variety classes pollutant, moreover, this hair
The bright filter membrane have very high porosity, vapour lock is extremely low, light transmission, ventilative, Non-energy-consumption, greatly reduce production run at
This, meanwhile, production method is simple and quick, can be widely applied in production and living.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the X-ray powder diffraction figure for the filter membrane that embodiment 1 obtains.
Fig. 2 is the scanning electron microscope (SEM) photograph for the filter membrane that embodiment 1 obtains.
Fig. 3 is the X-ray powder diffraction figure for the filter membrane that embodiment 2 obtains.
Fig. 4 is the scanning electron microscope (SEM) photograph for the filter membrane that embodiment 2 obtains.
Fig. 5 is the X-ray powder diffraction figure for the filter membrane that embodiment 3 obtains.
Fig. 6 is the scanning electron microscope (SEM) photograph for the filter membrane that embodiment 3 obtains.
Fig. 7 is the X-ray powder diffraction figure for the filter membrane that embodiment 4 obtains.
Fig. 8 is the scanning electron microscope (SEM) photograph for the filter membrane that embodiment 4 obtains.
Fig. 9 is the PM2.5 filtration result figure for the filter membrane that embodiment 1 obtains.
Figure 10 is the X-ray powder diffraction figure for the filter membrane that embodiment 11 obtains.
Figure 11 is the scanning electron microscope (SEM) photograph for the filter membrane that embodiment 11 obtains.
Figure 12 is the X-ray powder diffraction figure for the filter membrane that embodiment 12 obtains.
Figure 13 is the scanning electron microscope (SEM) photograph for the filter membrane that embodiment 12 obtains.
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, in the absence of explanation to the contrary, the volumetric quantities of the liquid or gas that use are 20 DEG C,
The numerical value of 1 normal atmosphere pressure.
Metal-organic framework materials
Metal organic framework part in filter membrane of the invention is formed by metal-organic framework materials, and the metal is organic
Framework material, which refers to be acted on by source metal and organic ligand, to be formed, and has an one-dimensional, two-dimentional or three-dimensional repeatable reticulated channel
The new material of structure.Wherein, source metal includes at least one of metal cluster, metal salt or metal oxide.
Metallic element in the source metal can be in Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge
At least one.
Wherein it is preferred to which the metallic element in the source metal of the metal-organic framework materials is Zn, Zr, Cu or Mg.
The organic ligand is、、、、、、OrOne of, or include following co-ordinating functionality :-CO2H、-NO2、-OH、-
NH2、-CN、-SO3H、-SH、-CH(RSH)2、-C(RSH)3、-CH(RNH2)2、-C(RNH2)3、-CH(ROH)2、-C(ROH)3、-CH
(RCN)2、-C(RCN)3、-CH(NH2)2、-C(NH2)3、-CH(CN)2Or C (CN)3At least one of, wherein co-ordinating functionality
In R be independently represented each other the alkylene comprising 1 to 5 phenyl ring.Wherein, preferred organic ligand isOr comprising-
CO2H、-NH2Or the organic ligand of at least one of-OH co-ordinating functionality.
The organic ligand includes terephthalic acid (TPA), trimesic acid, 2- nitroterephthalic, 2- hydroxyl terephthaldehyde
Acid, 2,5-Dihydroxyterephthalic acid, 2- amino terephthalic acid (TPA), 2- sulfonic group terephthalic acid (TPA) list sodium, 5- amino isophthalic two
Formic acid, 5- nitroisophthalic acid, 4 hydroxyisophthalic acid, 5- sulfonic group M-phthalic acid mono-sodium salt, benzoic acid, 4,4 '-
Biphenyl dicarboxylic acid, 2,2 '-dinitro -4,4 '-biphenyl dicarboxylic acids, 2,2 '-diamino -4,4 '-biphenyl dicarboxylic acids, 2,2 '-two
4,4 '-biphenyl dicarboxylic acid of hydroxyl-, 3,3 ', 5,5 '-bibenzene tetracarboxylics, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics, 2,6-naphthalenedicarboxylic acid, naphthalene-
Isosorbide-5-Nitrae-dioctyl phthalate, 3- mercaptopropionic acid, 3- amino -5- sulfydryl -1,2,4- triazole, 2,3-dimercaptosuccinic acid, 5- methoxyl group -2-
Mercaptobenzimidazole, 1- methyl -5- mercapto tetrazole, imidazoles, benzimidazole, 2-mercaptobenzimidazole, N, N- carbonyl dimidazoles,
1- methylimidazole, 2-ethyl-4-methylimidazole, 2,4- methylimidazole, 2-methylimidazole, 4-methylimidazole, 2- nitroimidazole,
2- cyanoimidazole, 1,2- methylimidazole, imidazole-4,5-dicarboxylic acid, 4- amino -5- Imidazole carboxamide, 2- methylol -1H- benzene
And imidazoles, 2- tolimidazole, 5,6- dimethylbenzimidazole, 4,5- dicyano imidazole, benzimidazole -5- formic acid, 1H- miaow
Azoles -4- formic acid, 2 isopropyl imidazole, 1 benzyl 2 methyl imidazole, 4- nitroimidazole, 5- aminotetrazole monohydrate, four nitrogen
Zole acetic acid, 1,2,4- triazoles, 1- methyl-1,2,4- triazoles, 1- methyl-1,2,3,4- tetrazoles, triazole -3- carboxylic acid,
4- amino -4H-1,2,4- triazoles, 3- nitro -1,2,4- triazole.
Metal-organic framework materials used in the present invention can be prepared with method in the prior art, be made in the present invention
Metal-organic framework materials the preparation method is as follows:
Method 1:
0.1250 gram of zirconium chloride is dissolved in 5 milliliters of n,N-Dimethylformamide (DMF), by 0.1340 gram
2- amino terephthalic acid (TPA) is dissolved in 10 milliliters of DMF, is then uniformly mixed two kinds of solution, and it is small that 12 are reacted under 80oC
When, the powder being centrifugally separating to obtain is washed 3 times with DMF, and is impregnated 3 days in ethanol, 150 oC of products therefrom drying.
Method 2:
0.60 gram of copper acetate and 0.42 gram of trimesic acid are put into ball grinder, 1 milliliter of ethyl alcohol, mechanical ball mill is added
30 minutes, blue solid is taken out, is washed several times with ethanol solution, until filtrate clarification, then 60 DEG C of drying, are produced
Object.
Method 3:
0.6454 gram of zinc nitrate and 0.8106 gram of 2-methylimidazole are dissolved in 50 ml methanols, at room temperature
24 hours are stood, white powder is centrifugally separating to obtain, is washed several times with methanol, 150 oC of products therefrom drying.
Method 4:
1.4 grams of magnesium nitrates and 0.337 gram of 2,5-Dihydroxyterephthalic acid are dissolved into 135 milliliters of N, N- dimethyl formyl
The in the mixed solvent of amine (DMF), 9 milliliters of ethyl alcohol and 9 milliliters of water, reacts 26 hours, obtained product first under 125oC
Alcohol washing, and impregnate in methyl alcohol 3 days, products therefrom is filtered later and 250 oC are dried 6 hours under vacuum conditions.
Polymer
Polymer of the present invention can be the various chemical substances that can be used for preparing membrane material, including polytetrafluoroethylene (PTFE),
Polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, polymethyl acrylate, poly- second two
At least one of alcohol, polycarbonate.Currently preferred polymer is polyacrylonitrile, polystyrene or polyvinylpyrrolidine
Ketone.
The preparation of filter membrane
Contact of the metal-organic framework materials of the present invention with polymer carries out in a solvent.
The solvent include water, methanol, ethyl alcohol, dimethylformamide, dimethyl acetamide, in diethylformamide extremely
Few one kind.The inventors discovered that selecting dimethylformamide as solvent, obtained film purity is higher, and filtration result is more preferable.
Relative to 1 gram of metal-organic framework materials, the dosage of the polymer can be 0.1-10 grams, more preferably
1-8 grams, the dosage of solvent is 10-100 milliliters, more preferably 15-80 milliliters.
Filter membrane of the invention is prepared by spinning process.
By on metal-organic framework materials and polymer spun to non-woven fabrics, the two interweaves growth so that obtaining metal has jointly
Machine skeleton/polymer filtration film.Specifically, first, in accordance with following parameter setting spinning machine: spinning feeding rate is 0.1-10 milli
Liter per hour, preferably 0.5-5 milliliter per hour, spinning voltage be 8-13 kilovolt, spinning distance be 10-50 centimetres, be preferably
15-30 centimetres, the spinning time is 1-30 minutes, preferably 3-20 minutes, needle sizes 20G.Later by gold of the present invention
Belong to organic framework material and polymer contacts the spinning solution injection sample introduction needle of formation in a solvent, non-woven fabrics is put as substrate is received
Cathode is placed in for receiving the spinning solution sprayed.Spinning solution is ejected into non-woven fabrics according to certain rate of feed by starting device
On, obtain filter membrane of the invention.
Filter membrane of the invention can also be prepared by the method for dip-coating.
Specifically, by metal-organic framework materials of the present invention with polymer in a solvent contact formation mixing it is molten
Mixed solution is placed in controllable temperature oil bath pan by liquid, and temperature control is constant to be stirred continuously at 25 degrees Celsius of room temperature, later mixed
It closes and is immersed in solution as the non-woven fabrics for receiving substrate, after each dip-coating 30 seconds to 5 minutes, dip-coating 1-10 times, take out non-woven fabrics
75 degrees Celsius of dry half an hour are in an oven up to filter membrane of the invention.
PM2.5's filters out test
Following equipment, title: four-in-one corpuscular counter, model: DT- are used to the test of PM2.5 in the present invention
9881M, manufacturer: Shenzhen Huashengchang Machinary Industry Co., Ltd.PM2.5 concentration can be directly tested using the equipment to become
Change.
Wherein, described to filter out PM2.5 measure of merit condition are as follows: 30 min are tested under normal temperature and pressure.
Volatile organic compounds filters out test
The test method of volatile organic compounds are as follows: first by the formaldehyde or toluene vapor of certain volume concentration X1 ppm
By closed film filter, device exhaust end is accessed quadrupole rod mass spectrometer, and (producer: Beijing Ying Gehaide analyzes skill
Art Co., Ltd) test of quantitative analysis is carried out, obtain object volumetric concentration X2 ppm.By calculation formula (X1-X2)/X1*
100%, it obtains filtering out efficiency.
Wherein, described to filter out volatile organic compounds measure of merit condition are as follows: 115 ppm of input concentration, gas flow rate
150 sccm, vacuum condition scan 5 minutes.
Present invention be described in more detail by the following examples.
Embodiment 1
Metal-organic framework materials (source metal is zirconium chloride, organic ligand is 2- amino terephthalic acid (TPA)) are dispersed in molten
In agent dimethylformamide, polyacrylonitrile is added, is uniformly mixed, obtains spinning solution.Wherein, the metal relative to 1 gram is organic
Framework material, the dosage of polymer are 5 grams, and the dosage of solvent is 50 milliliters, and mixing temperature is room temperature, and incorporation time is 8 small
When.
Above-mentioned spinning solution is subjected to spinning, fiber is received with non-woven fabrics, obtains filter membrane；Wherein, spinning parameter is spinning
Per hour, spinning voltage is 13 kilovolts to 3 milliliters of rate of feed, and spinning distance is 20 centimetres, and the spinning time is 10 minutes, needle type
Number be 20 G.
X-ray powder diffraction and scanning electron microscope analysis are carried out to the filter membrane.X-ray powder diffraction, model: Bruker
D8 Advance tests section 4-500, scanning speed 40Per minute；Scanning electron microscope model Hitachi S4800, sweep parameter:
1, Fig. 2A, 5 kilovolts of acceleration voltage, 9.3 millimeters of operating distance, 4.5 ten thousand times of amplification factor, 10 microns of length scales；2, Fig. 2 B adds
5 kilovolts of fast voltage, 9.3 millimeters of operating distance, 450,000 times of amplification factor, 1 micron of length scales.Metal organic framework as the result is shown
Material is able to maintain original structure, and filter membrane successfully is obtained with polymer spinning.The X-ray powder diffraction figure of the filter membrane is such as
Shown in Fig. 1, scanning electron microscope (SEM) photograph is as shown in Figure 2 A and 2 B.
In Fig. 1, the nanometer that is obtained after the metal-organic framework materials of synthesis, metal-organic framework materials and mixed with polymers
The monocrystalline simulation curve of fiber and metal-organic framework materials fits like a glove, and illustrates successfully to synthesize to have obtained corresponding metal organic
Skeleton structure, and the metal-organic framework materials on filter membrane maintain original structure, are not destroyed；Fig. 2A and Fig. 2 B
In, it is the scanning electron microscope (SEM) photograph done to gained filter membrane, passes through electron microscope, it can be seen that metal-organic framework materials and polymer spun
Silk has successfully obtained nanofiber, and in forming netted intertexture on non-woven fabrics, obtains filter membrane.Wherein, the line of intertexture is polymerization
Fiber, the protrusion on line is metal-organic framework materials.
Embodiment 2
Metal-organic framework materials (source metal is copper acetate, organic ligand is trimesic acid) are dispersed in dimethyl methyl
In amide, polystyrene is added, is uniformly mixed, obtains spinning solution.Wherein, relative to 1 gram of metal-organic framework materials,
The dosage of polymer is 8 grams, and the dosage of solvent is 80 milliliters, and mixing temperature is room temperature, and incorporation time is 8 hours.
Above-mentioned spinning solution is subjected to spinning, fiber is received with non-woven fabrics, obtains filter membrane；Wherein, spinning parameter is spinning
Per hour, spinning voltage is 10 kilovolts to 5 milliliters of rate of feed, and spinning distance is 15 centimetres, and the spinning time is 5 minutes, syringe needle model
For 20 G.
X-ray powder diffraction and scanning electron microscope analysis, test method and the same embodiment of test condition are carried out to the filter membrane
1, metal-organic framework materials are able to maintain original structure as the result is shown, and filter membrane successfully is obtained with polymer spinning.The mistake
The X-ray powder diffraction figure of filter membrane is as shown in figure 3, scanning electron microscope (SEM) photograph is as shown in Figure 4 A and 4 B shown in FIG..In Fig. 3, the metal of synthesis has
The list of the nanofiber and metal-organic framework materials that are obtained after machine framework material, metal-organic framework materials and mixed with polymers
Brilliant simulation curve fits like a glove, and illustrates successfully to synthesize to have obtained corresponding metallo-organic framework, and the gold on filter membrane
Belong to organic framework material to maintain original structure, be not destroyed；It is the scanning electricity done to gained filter membrane in Fig. 4 A and Fig. 4 B
Mirror figure, passes through electron microscope, it can be seen that metal-organic framework materials and polymer spinning have successfully obtained nanofiber, and in nothing
Netted intertexture is formed in woven fabric, obtains filter membrane.Wherein, the line of intertexture is polymer fiber, and the protrusion on line is the organic bone of metal
Frame material.
Embodiment 3
Metal-organic framework materials (source metal is zinc nitrate, and organic ligand is 2-methylimidazole) are dispersed in dimethyl methyl
In amide, polyacrylonitrile is added, is uniformly mixed, obtains spinning solution.Wherein, relative to 1 gram of metal-organic framework materials,
The dosage of polymer is 3 grams, and the dosage of solvent is 35 milliliters, and mixing temperature is room temperature, and incorporation time is 8 hours.
Above-mentioned spinning solution is subjected to spinning, fiber is received with non-woven fabrics, obtains filter membrane；Wherein, spinning parameter is spinning
Per hour, spinning voltage is 12 kilovolts to 2 milliliters of rate of feed, and spinning distance is 30 centimetres, and the spinning time is 3 minutes, syringe needle model
For 20 G.
X-ray powder diffraction and scanning electron microscope analysis, test method and the same embodiment of test condition are carried out to the filter membrane
1, metal-organic framework materials are able to maintain original structure as the result is shown, and filter membrane successfully is obtained with polymer spinning.The mistake
The X-ray powder diffraction figure of filter membrane is as shown in figure 5, scanning electron microscope (SEM) photograph is as shown in Figure 6 A and 6 B.In Fig. 5, the metal of synthesis has
The list of the nanofiber and metal-organic framework materials that are obtained after machine framework material, metal-organic framework materials and mixed with polymers
Brilliant simulation curve fits like a glove, and illustrates successfully to synthesize to have obtained corresponding metallo-organic framework, and the gold on filter membrane
Belong to organic framework material to maintain original structure, be not destroyed；It is the scanning electricity done to gained filter membrane in Fig. 6 A and Fig. 6 B
Mirror figure, passes through electron microscope, it can be seen that metal-organic framework materials and polymer spinning have successfully obtained nanofiber, and in nothing
Netted intertexture is formed in woven fabric, obtains filter membrane.Wherein, the line of intertexture is polymer fiber, and the protrusion on line is the organic bone of metal
Frame material.
Embodiment 4
Metal-organic framework materials (source metal is magnesium nitrate, and organic ligand is 2,5-Dihydroxyterephthalic acid) is dispersed
In dimethylformamide, polyvinylpyrrolidone is added, is uniformly mixed, obtains spinning solution.Wherein, relative to 1 gram of gold
Belong to organic framework material, the dosage of polymer is 5 grams, and the dosage of solvent is 50 milliliters, and mixing temperature is room temperature, incorporation time
It is 8 hours.
Above-mentioned spinning solution is subjected to spinning, fiber is received with non-woven fabrics, obtains filter membrane；Wherein, spinning parameter is spinning
Per hour, spinning voltage is 8 kilovolts to 0.5 milliliter of rate of feed, and spinning distance is 15 centimetres, and the spinning time is 20 minutes, needle type
Number be 20 G.
X-ray powder diffraction and scanning electron microscope analysis, test method and the same embodiment of test condition are carried out to the filter membrane
1, metal-organic framework materials are able to maintain original structure as the result is shown, and filter membrane successfully is obtained with polymer spinning.The mistake
The X-ray powder diffraction figure of filter membrane is as shown in fig. 7, scanning electron microscope (SEM) photograph is as shown in Figure 8 A and 8 B.In Fig. 7, the metal of synthesis has
The list of the nanofiber and metal-organic framework materials that are obtained after machine framework material, metal-organic framework materials and mixed with polymers
Brilliant simulation curve fits like a glove, and illustrates successfully to synthesize to have obtained corresponding metallo-organic framework, and the gold on filter membrane
Belong to organic framework material to maintain original structure, be not destroyed；It is the scanning electricity done to gained filter membrane in Fig. 8 A and Fig. 8 B
Mirror figure, passes through electron microscope, it can be seen that metal-organic framework materials and polymer spinning have successfully obtained nanofiber, and in nothing
Netted intertexture is formed in woven fabric, obtains filter membrane.Wherein, the line of intertexture is polymer fiber, and the protrusion on line is the organic bone of metal
Frame material.
Embodiment 5-10
Filter membrane, design parameter and raw material is prepared in table 1 according to the method for embodiment 1,2,3 and 4 to record.
Embodiment 11
Metal-organic framework materials (source metal is zinc nitrate, and organic ligand is 2-methylimidazole) are dispersed in dimethyl methyl
In amide, polyacrylonitrile is added, is uniformly mixed, obtains mixed solution.Wherein, relative to 1 gram of metal organic framework material
Material, the dosage of polymer are 3 grams, and the dosage of solvent is 35 milliliters.Non-woven fabrics is as receiving in substrate merging mixed solution, often
It after secondary dip-coating 30 seconds, dip-coating 10 times, takes out, being put into 75 degrees Celsius of dry half an hour in baking oven obtains filter membrane.To the filter membrane
X-ray powder diffraction and scanning electron microscope analysis, test method and test condition are carried out with embodiment 3, gained test result is shown in figure
10-11.The present embodiment is tested by the method for filtering out test of description of the invention PM2.5 above-mentioned and volatile organic compounds
Obtained filter membrane, result are that filter out efficiency be 89.7% to PM2.5, and the efficiency that filters out of formaldehyde is 89.3%, and toluene filters out efficiency
It is 87.1%.
Embodiment 12
Metal-organic framework materials (source metal is magnesium nitrate, and organic ligand is 2,5-Dihydroxyterephthalic acid) is dispersed
In dimethylformamide, polyvinylpyrrolidone is added, is uniformly mixed, obtains mixed solution.Wherein, relative to 1 gram
Metal-organic framework materials, the dosage of polymer are 5 grams, and the dosage of solvent is 50 milliliters.Non-woven fabrics is set as substrate is received
Enter in mixed solution, each dip-coating is put into 75 degrees Celsius of dry half an hour in baking oven and obtains filter membrane after 5 minutes, dip-coating 1 time.It is right
The filter membrane carries out X-ray powder diffraction and scanning electron microscope analysis, test method and test condition with embodiment 4, test result
See Figure 12-13, tests this reality by the method for filtering out test of description of the invention PM2.5 above-mentioned and volatile organic compounds
The filter membrane that example obtains is applied, the efficiency that filters out that result is PM2.5 is 92.2%, and the efficiency that filters out of formaldehyde is 91.5%, the filter of toluene
Except efficiency is 89.9%.
Test case 1
By the obtained filter membrane of the method testing example 1-10 for filtering out test of description of the invention PM2.5 above-mentioned
PM2.5 performance is filtered out, specifically filters out efficiency data referring to table 1.
There are a large amount of apparent protrusions in Fig. 9, on polymer fiber, these protrusions are the PM2.5 of polymer fiber capture.
Test case 2
It is obtained by the method testing example 1-10 for filtering out test of description of the invention volatile organic compounds above-mentioned
To filter membrane the performance for filtering out formaldehyde, specifically filter out efficiency data referring to table 1.
Test case 3
It is obtained by the method testing example 1-10 for filtering out test of description of the invention volatile organic compounds above-mentioned
To filter membrane the performance for filtering out toluene, specifically filter out efficiency data referring to table 1.
The parameter of 1 embodiment 1-10 of table and PM's 2.5, formaldehyde and toluene filters out efficiency
According to the data of Fig. 1-13 as it can be seen that process of the invention can successfully obtain filter membrane；Pass through embodiment 1-
12 filter out efficiency data as it can be seen that the filter membrane that method of the invention is prepared can be filtered out rapidly and efficiently and PM2.5 and be waved
Hair property organic compound.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (28)
1. a kind of filter membrane, is formed by metal-organic framework materials and polymer, the metal-organic framework materials form described
Metal organic framework part in filter membrane, the polymer form the polymer fiber part in the filter membrane, and described
Metal-organic framework materials and the polymer form nanofiber, and the line in the nanofiber is polymer fiber, described poly-
Protrusion on condensating fiber is metal-organic framework materials, wherein the metal-organic framework materials are made by source metal and organic ligand
With formation, relative to 1 gram of the metal-organic framework materials, the dosage of the polymer is 0.1-10 grams, the filtering
Film is 80% or more to 30 minutes rejection rates of PM2.5 and volatile organic compounds.
2. filter membrane described in claim 1, which is characterized in that the source metal includes metal cluster, metal salt or metal oxygen
At least one of compound.
3. filter membrane as claimed in claim 2, which is characterized in that the metallic element in the source metal include Mg, Ca, Zr, Cr,
At least one of Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge.
4. filter membrane as claimed in claim 3, which is characterized in that the metallic element includes at least one in Zn, Zr, Cu or Mg
Kind.
5. filter membrane described in claim 1, which is characterized in that the organic ligand is、、、、、、Or
One of, or include following co-ordinating functionality :-CO2H、-NO2、-OH、-NH2、-CN、-SO3H、-SH、-CH(RSH)2、-C
(RSH)3、-CH(RNH2)2、-C(RNH2)3、-CH(ROH)2、-C(ROH)3、-CH(RCN)2、-C(RCN)3、-CH(NH2)2、-C
(NH2)3、-CH(CN)2Or-C (CN)3At least one of, wherein the R in co-ordinating functionality be independently represented each other comprising 1 to
The alkylene of 5 phenyl ring.
6. filter membrane described in claim 5, which is characterized in that the organic ligand isOr include-CO2H、-NH2
Or the organic ligand of at least one of-OH co-ordinating functionality.
7. filter membrane described in claim 1, which is characterized in that the polymer includes polytetrafluoroethylene (PTFE), polystyrene, polychlorostyrene
Ethylene, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, polymethyl acrylate, polyethylene glycol, in polycarbonate
At least one.
8. filter membrane as claimed in claim 7, which is characterized in that the polymer is polyacrylonitrile, polystyrene or polyethylene
Pyrrolidones.
9. filter membrane described in claim 1, which is characterized in that the source metal of the metal-organic framework materials be zirconium chloride,
Organic ligand is 2- amino terephthalic acid (TPA), and the polymer is polyacrylonitrile.
10. filter membrane described in claim 1, which is characterized in that the source metal of the metal-organic framework materials be copper acetate,
Organic ligand is trimesic acid, and the polymer is polystyrene.
11. filter membrane described in claim 1, which is characterized in that the source metal of the metal-organic framework materials be zinc nitrate,
Organic ligand is 2-methylimidazole, and the polymer is polyacrylonitrile.
12. filter membrane described in claim 1, which is characterized in that the source metal of the metal-organic framework materials be magnesium nitrate,
Organic ligand is 2,5-Dihydroxyterephthalic acid, and the polymer is polyvinylpyrrolidone.
13. a kind of method for preparing filter membrane, this method comprises: by metal-organic framework materials and polymer contact, the gold
Belong to organic framework material and form the metal organic framework part in the filter membrane, the polymer is formed in the filter membrane
Polymer fiber part, and the metal-organic framework materials and the polymer form nanofiber, in the nanofiber
Line be polymer fiber, the protrusion on the polymer fiber is metal-organic framework materials, wherein the metal organic framework material
Material, which is acted on by source metal with organic ligand, to be formed, relative to 1 gram of the metal-organic framework materials, the use of the polymer
Amount is 0.1-10 grams, and the filter membrane is 80% or more to 30 minutes rejection rates of PM2.5 and volatile organic compounds.
14. method described in claim 13, it is characterised in that: the source metal includes metal cluster, metal salt or metal oxygen
At least one of compound.
15. method of claim 14, it is characterised in that: the metallic element in the source metal include Mg, Ca, Zr, Cr,
At least one of Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge.
16. method of claim 15, which is characterized in that the metallic element includes at least one in Zn, Zr, Cu or Mg
Kind.
17. method described in claim 13, it is characterised in that: the organic ligand is、、、、、、Or
One of, or include following co-ordinating functionality :-CO2H、-NO2、-OH、-NH2、-CN、-SO3H、-SH、-CH(RSH)2、-C
(RSH)3、-CH(RNH2)2、-C(RNH2)3、-CH(ROH)2、-C(ROH)3、-CH(RCN)2、-C(RCN)3、-CH(NH2)2、-C
(NH2)3、-CH(CN)2Or-C (CN)3At least one of, wherein the R in co-ordinating functionality be independently represented each other comprising 1 to
The alkylene of 5 phenyl ring.
18. method described in claim 17, which is characterized in that the organic ligand isOr include-CO2H、-OH
Or-NH2At least one of co-ordinating functionality organic ligand.
19. method described in claim 13, it is characterised in that: the polymer includes polytetrafluoroethylene (PTFE), polystyrene, polychlorostyrene
Ethylene, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, polymethyl acrylate, polyethylene glycol, in polycarbonate
At least one.
20. method described in claim 19, which is characterized in that the polymer is polyacrylonitrile, polystyrene or polyethylene
Pyrrolidones.
21. method described in claim 13, which is characterized in that the source metal of the metal-organic framework materials be zirconium chloride,
Organic ligand is 2- amino terephthalic acid (TPA), and the polymer is polyacrylonitrile.
22. method described in claim 13, which is characterized in that the source metal of the metal-organic framework materials be copper acetate,
Organic ligand is trimesic acid, and the polymer is polystyrene.
23. method described in claim 13, which is characterized in that the source metal of the metal-organic framework materials be zinc nitrate,
Organic ligand is 2-methylimidazole, and the polymer is polyacrylonitrile.
24. method described in claim 13, which is characterized in that the source metal of the metal-organic framework materials be magnesium nitrate,
Organic ligand is 2,5-Dihydroxyterephthalic acid, and the polymer is polyvinylpyrrolidone.
25. according to the method for claim 13, it is characterised in that: contact of the metal-organic framework materials with polymer
It carries out in a solvent, opposite 1 gram of metal-organic framework materials, the dosage of solvent is 10-100 milliliters, passes through spinning or leaching
Coating method prepares the filter membrane.
26. according to the method for claim 25, it is characterised in that: the solvent includes water, methanol, ethyl alcohol, dimethyl methyl
At least one of amide, dimethyl acetamide, diethylformamide.
27. any one of filter membrane or claim 13-26 right described in claim 1-12 any one claim
It is required that filter membrane prepared by the method is filtering out the purposes in PM2.5.
28. any one of filter membrane or claim 13-26 right described in claim 1-12 any one claim
It is required that filter membrane prepared by the method is filtering out the purposes in volatile organic compounds.
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| CN106328236B (en) * | 2016-09-21 | 2018-02-16 | 中国科学院高能物理研究所 | The material of Exemplary radionuclides and its application in a kind of processing waste water |
| CN107880277B (en) * | 2017-12-05 | 2021-08-31 | 池州学院 | Two-dimensional zinc coordination polymer and preparation method thereof |
| KR102039243B1 (en) * | 2018-02-13 | 2019-10-31 | 한국과학기술원 | Particulate matter filter and member using two dimensional hierarchical metal-organic framework functionalized on membrane, and manufacturing method thereof |
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