CN117946355B - Preparation method and application of asymmetric self-supporting covalent organic framework film - Google Patents
Preparation method and application of asymmetric self-supporting covalent organic framework film Download PDFInfo
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- CN117946355B CN117946355B CN202410359809.7A CN202410359809A CN117946355B CN 117946355 B CN117946355 B CN 117946355B CN 202410359809 A CN202410359809 A CN 202410359809A CN 117946355 B CN117946355 B CN 117946355B
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- organic framework
- covalent organic
- dicarboxaldehyde
- solution
- film
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 239000012074 organic phase Substances 0.000 claims abstract description 36
- 239000008346 aqueous phase Substances 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- 238000012546 transfer Methods 0.000 claims abstract description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 87
- 239000000243 solution Substances 0.000 claims description 55
- 239000012528 membrane Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 18
- 150000001447 alkali salts Chemical class 0.000 claims description 16
- 150000001299 aldehydes Chemical class 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- -1 4' -biphenyldiamine Chemical compound 0.000 claims description 8
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 7
- 229930187593 rose bengal Natural products 0.000 claims description 7
- 229940081623 rose bengal Drugs 0.000 claims description 7
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 claims description 7
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 7
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 6
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- 229920005597 polymer membrane Polymers 0.000 claims description 6
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 5
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical group NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 5
- 229940097275 indigo Drugs 0.000 claims description 5
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920001744 Polyaldehyde Polymers 0.000 claims description 3
- 239000004098 Tetracycline Substances 0.000 claims description 3
- 229930003779 Vitamin B12 Natural products 0.000 claims description 3
- 229960003405 ciprofloxacin Drugs 0.000 claims description 3
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 claims description 3
- ZMMJGEGLRURXTF-UHFFFAOYSA-N ethidium bromide Chemical compound [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 ZMMJGEGLRURXTF-UHFFFAOYSA-N 0.000 claims description 3
- 229960005542 ethidium bromide Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229960002180 tetracycline Drugs 0.000 claims description 3
- 229930101283 tetracycline Natural products 0.000 claims description 3
- 235000019364 tetracycline Nutrition 0.000 claims description 3
- 150000003522 tetracyclines Chemical class 0.000 claims description 3
- 239000011715 vitamin B12 Substances 0.000 claims description 3
- 235000019163 vitamin B12 Nutrition 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 2
- WJHRAPYKYJKACM-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalaldehyde Chemical compound FC1=C(F)C(C=O)=C(F)C(F)=C1C=O WJHRAPYKYJKACM-UHFFFAOYSA-N 0.000 claims description 2
- VSUKSWCSOBXUFG-UHFFFAOYSA-N 2,5-dibromoterephthalaldehyde Chemical compound BrC1=CC(C=O)=C(Br)C=C1C=O VSUKSWCSOBXUFG-UHFFFAOYSA-N 0.000 claims description 2
- XBCGIUJJUZHWMC-UHFFFAOYSA-N 2,5-dichloroterephthalaldehyde Chemical compound ClC1=CC(C=O)=C(Cl)C=C1C=O XBCGIUJJUZHWMC-UHFFFAOYSA-N 0.000 claims description 2
- QIUMSVLKXTWDSN-UHFFFAOYSA-N 2,5-difluoroterephthalaldehyde Chemical compound FC1=CC(C=O)=C(F)C=C1C=O QIUMSVLKXTWDSN-UHFFFAOYSA-N 0.000 claims description 2
- PIWMYUGNZBJTID-UHFFFAOYSA-N 2,5-dihydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=C(O)C=C1C=O PIWMYUGNZBJTID-UHFFFAOYSA-N 0.000 claims description 2
- YSIIHTHHMPYKFP-UHFFFAOYSA-N 2,5-dimethoxyterephthalaldehyde Chemical compound COC1=CC(C=O)=C(OC)C=C1C=O YSIIHTHHMPYKFP-UHFFFAOYSA-N 0.000 claims description 2
- AIBJDPZNCNFKMR-UHFFFAOYSA-N 2,5-dimethylterephthalaldehyde Chemical compound CC1=CC(C=O)=C(C)C=C1C=O AIBJDPZNCNFKMR-UHFFFAOYSA-N 0.000 claims description 2
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 claims description 2
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical compound [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 claims description 2
- DFIOBSJHIZBUCE-UHFFFAOYSA-N 2-hydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=CC=C1C=O DFIOBSJHIZBUCE-UHFFFAOYSA-N 0.000 claims description 2
- KYERQSUZHFINIE-UHFFFAOYSA-N 4-[2,4,5-tris(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC(C=2C=CC(C=O)=CC=2)=C(C=2C=CC(C=O)=CC=2)C=C1C1=CC=C(C=O)C=C1 KYERQSUZHFINIE-UHFFFAOYSA-N 0.000 claims description 2
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 2
- YCZUWQOJQGCZKG-UHFFFAOYSA-N 9h-carbazole-3,6-diamine Chemical compound C1=C(N)C=C2C3=CC(N)=CC=C3NC2=C1 YCZUWQOJQGCZKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017917 NH4 Cl Inorganic materials 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- REPFNYFEIOZRLM-UHFFFAOYSA-N chembl376444 Chemical compound C1=CC(N)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(N)=CC=1)=C1C=CC(=N1)C(C=1C=CC(N)=CC=1)=C1C=CC(N1)=C1C=2C=CC(N)=CC=2)=C2N=C1C=C2 REPFNYFEIOZRLM-UHFFFAOYSA-N 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- UBKNFAFBINVTOP-UHFFFAOYSA-N thieno[3,2-b]thiophene-2,5-dicarbaldehyde Chemical compound S1C(C=O)=CC2=C1C=C(C=O)S2 UBKNFAFBINVTOP-UHFFFAOYSA-N 0.000 claims description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007873 sieving Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 2
- 239000010408 film Substances 0.000 description 63
- 150000001450 anions Chemical class 0.000 description 34
- 229920006254 polymer film Polymers 0.000 description 22
- 239000002585 base Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 11
- 229960001553 phloroglucinol Drugs 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920000620 organic polymer Polymers 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- OJUDFURAIYFYBP-UHFFFAOYSA-N (dihydrazinylmethylideneamino)azanium;chloride Chemical compound Cl.NNC(NN)=NN OJUDFURAIYFYBP-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- MBJAPGAZEWPEFB-UHFFFAOYSA-N 5-amino-2-(4-amino-2-sulfophenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C1=CC=C(N)C=C1S(O)(=O)=O MBJAPGAZEWPEFB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- LJCZNYWLQZZIOS-UHFFFAOYSA-N 2,2,2-trichlorethoxycarbonyl chloride Chemical compound ClC(=O)OCC(Cl)(Cl)Cl LJCZNYWLQZZIOS-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- JQXXHWHPUNPDRT-YOPQJBRCSA-N chembl1332716 Chemical compound O([C@](C1=O)(C)O\C=C/[C@@H]([C@H]([C@@H](OC(C)=O)[C@H](C)[C@H](O)[C@H](C)[C@@H](O)[C@@H](C)/C=C\C=C(C)/C(=O)NC=2C(O)=C3C(O)=C4C)C)OC)C4=C1C3=C(O)C=2\C=N\N1CCN(C)CC1 JQXXHWHPUNPDRT-YOPQJBRCSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003075 phytoestrogen Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229960001225 rifampicin Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003270 steroid hormone Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- 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
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Abstract
The invention discloses a preparation method and application of an asymmetric self-supporting covalent organic framework film, wherein an aqueous phase-organic phase two-phase interface method is adopted to carry out polycondensation reaction on an aqueous phase containing an amine monomer and an organic phase containing an aldehyde monomer at an interface to obtain the asymmetric self-supporting covalent organic framework film; inorganic salt is added in the aqueous phase system, and the reaction of the amine monomer and the aldehyde monomer in the organic phase is accelerated by the synergistic effect of accelerating the mass transfer of the amine monomer in the aqueous phase and coordination pre-assembly. The scheme of the invention enables the polymerization reaction which cannot be carried out at normal temperature and normal pressure to be carried out under the pushing action of inorganic salt, and has the advantages of high reaction rate and high yield. In addition, the covalent organic framework film prepared by the method has the characteristics of good crystallinity, high porosity, good mechanical property and chemical stability, and excellent molecular sieving capability.
Description
Technical Field
The invention belongs to the technical field of new material films, and particularly relates to a preparation method and application of an asymmetric self-supporting covalent organic framework film.
Background
Covalent organic framework high molecular materials (COFs) are regarded as one of the most advanced materials in the 21 st century as new generation crystal framework polymer materials, and have ultrahigh specific surface area, regular and periodic pore structures, narrower pore size distribution, good chemical stability and excellent designability, and can be used for constructing primitive chemical structure diversity, endowing the COFs with various topological structures, enabling the pore size to be precisely regulated and controlled on the sub-nanometer scale, facilitating functionalization and endowing the COFs with new functions. COFs polymeric materials are widely used in adsorption, separation, catalysis, proton conduction, and the like.
Organic pollutants such as organic dyes and newly-appearing trace organic pollutants (TrOCs) have increasingly serious effects on natural waterways and aquatic ecosystems, and have raised potential threats to human health and the health of aquatic environments, which have attracted great attention. Of particular concern is TrOCs, a type of contaminant that currently lacks relevant environmental regulatory policies or emissions standards. Such contaminants include steroid hormones, phytoestrogens, endocrine disrupting chemicals, pharmaceutical and personal care products, industrial chemicals, disinfection byproducts, pesticides, and the like. TrOCs is difficult to remove from aquatic environments due to its low molecular weight, high toxicity, and high durability.
Membrane technology provides a promising and sustainable method for removing these contaminants from aqueous environments. However, most commercial membranes have pore sizes larger than the molecular size of most trace organic contaminants, and thus achieving effective interception is challenging. Current COFs films exhibit excellent ability to remove water and contaminants in organic solvents such as dyes, drugs and hydrated ions. However, COFs frameworks are composed of building blocks typically 0.8 to 5 nanometers, and their inherent pore size presents challenges for recognition of smaller TrOC through COFs channels.
Most COFs reactions require reactions under high temperature and high pressure conditions, and the resulting powder materials are difficult to reuse for many times. The COFs film can be repeatedly used as an emerging film material, can be recycled, and has a huge application prospect. The types of COFs films are mainly classified into imines, triazines, SPs 2, hydrazones, borates and the like according to different bonding types, and the COFs films of the types often need high temperature and high pressure and the presence of a catalyst to react, so that great difficulty is brought to the preparation of COFs. Among them, the difficulty for preparing ionic COFs films is far greater than that of nonionic COFs films. In general, interfacial polymerization techniques for fabricating non-ionic COFs films are difficult to migrate directly into ionic COFs film fabrication. According to the literature, it is reported that the ionic COFs film prepared by the interfacial polymerization strategy takes at least 15 days, and the crystallinity of the obtained ionic COFs film is very poor, and even more, the ionic COFs film cannot be obtained at all. The strong electron-withdrawing effect and the steric hindrance effect of the ionic groups carried by the monomers greatly reduce the reactivity of the monomers, so that the COFs film cannot be prepared through interface reaction. In addition, COFs membranes obtained by conventional methods are symmetrical, which is detrimental to molecular separation.
The above information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention provides a preparation method and application of an asymmetric self-supporting covalent organic framework film aiming at the defects of the prior art. The method for preparing the asymmetric COFs film is simple, convenient and controllable, high in efficiency and excellent in product quality, and the prepared COFs film has high crystallinity, excellent stability and film forming property. Meanwhile, the COFs membrane has an asymmetric special structure, and the asymmetric structure can increase the pore diameter gradient difference of the upper surface and the lower surface, thereby being beneficial to enhancing the flux increase during molecular separation and simultaneously having excellent molecular sieving capability.
The invention relates to a preparation method of an asymmetric self-supporting covalent organic framework film, which is obtained by performing polycondensation reaction on an aqueous phase containing amine monomers and an organic phase containing aldehyde monomers at an interface by a two-phase interface method of aqueous phase and organic phase; inorganic salt is added in the aqueous phase system, and the reaction of the amine monomer and the aldehyde monomer in the organic phase is accelerated by the synergistic effect of accelerating the mass transfer of the amine monomer in the aqueous phase and coordination pre-assembly.
The amine monomer is an amine monomer with an anionic group (including an anionic group such as-SO 3 H), a cationic group (-N +, etc.) or a neutral group.
Further, the amine monomer is selected from the group consisting of 2, 5-diaminobenzenesulfonic acid, 2, 4-diaminobenzenesulfonic acid, 4' -diaminobiphenyl-2, 2' -dicarboxylic acid, 4' -diaminobiphenyl-2, 2' -disulfonic acid, 4' -diamino-1, 1' -biphenyl-3, 3' -dicarboxylic acid, p-phenylenediamine, 4' -biphenyldiamine, 3, 5-diamino-1, 2, 4-triazole, 9H-carbazole-3, 6-diamine, 4' -azobis-aniline one of 1,3, 5-tris (4-aminophenyl) benzene, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, tris (4-aminophenyl) amine, trans-1, 4-cyclohexanediamine, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9-bis (4-aminophenyl) fluorene, ethidium bromide, tris aminoguanidine hydrochloride, hydrazine hydrate, tris (2-aminoethyl) amine.
Still further, the amine monomer is 2, 5-diaminobenzenesulfonic acid, 2, 4-diaminobenzenesulfonic acid, 4' -diaminobiphenyl-2, 2' -disulfonic acid, p-phenylenediamine, 4' -biphenyldiamine, ethidium bromide, or triaminoguanidine hydrochloride.
The aldehyde monomer is selected from the group consisting of triallylmethanol, trimellitic aldehyde, thieno [3,2-b ] thiophene-2, 5-dicarboxaldehyde, 2-hydroxy-1, 3, 5-benzene tricaldehyde, 2-hydroxybenzene-1, 4-dicarboxaldehyde, 2, 5-difluoro-terephthalaldehyde, 2, 5-dimethoxy benzene-1, 4-dicarboxaldehyde, 2, 5-dichloro-terephthalaldehyde, 2, 5-dibromobenzene-1, 4-dicarboxaldehyde, 2, 5-dimethyl-terephthalaldehyde, tetrafluoroterephthalaldehyde, 5,10,15, 20-tetrakis (4-aldyl benzene) -21H, 23H-porphyrin, 4 '-biphenyl-dicarboxaldehyde, 2, 5-dihydroxy-1, 4-benzene dicarboxaldehyde, 2-bipyridine-4, 4-dicarboxaldehyde, 1,2,4, 5-tetrakis (4-formylphenyl) benzene, 4' - (2, 2-bis 4-formylphenoxy) methyl) propane-1, 3-diyl) bis (oxy)) of the bis (oxy) benzene.
Further, the aldehyde monomer is trialdehyde phloroglucinol or trimesic aldehyde.
The solvents of the organic phases are all methylene dichloride.
The inorganic salts are readily soluble in water.
The invention discloses a preparation method of an asymmetric self-supporting covalent organic framework film, which comprises the following steps:
Step 1: respectively dissolving an amine monomer and inorganic salt in an aqueous solution, and then mixing the two to obtain an aqueous solution, wherein the inorganic salt provides a driving force to promote the amine monomer to accelerate mass transfer; dissolving polybasic aldehyde in dichloromethane to obtain an organic phase solution;
Step 2: adding an organic phase solution into the reactor, slowly adding the aqueous phase solution above the organic phase solution along the edge of the reactor, and standing at room temperature for reaction for 0.5-12 hours;
Step 3: and sucking water and methylene dichloride solution in the reaction system to obtain a covalent organic framework polymer film at the interface, respectively adding methylene dichloride, ethanol and aqueous solution to wash out excessive monomers, salt and solvent, and then placing the film in water to obtain the ionic or neutral covalent organic framework polymer film.
In the step 1, the molar concentration of the inorganic salt in the aqueous phase solution is 1-10mmol/L, and the molar concentration of the amine monomer is 0.1-9 mmol/L. The molar concentration of the polyaldehyde monomer in the organic phase solution is 0.1-9 mmol/L.
Further, the molar ratio of amine monomer to aldehyde monomer is preferably 3:2.
In the step 1, the inorganic salt is a strong acid and strong alkali salt or a strong acid and weak alkali salt, the strong acid and strong alkali salt is one or more selected from Na 2SO4、NaCl、NaNO3, and the strong acid and weak alkali salt is one or more selected from (NH 4)2SO4、NH4NO3、NH4 Cl).
In the step 1, the ratio of the inorganic salt to water is limited, and is preferably (1 mmol:80 mL) to (10 mmol:40 mL).
In step 1, the molar ratio of inorganic salt to amine monomer is preferably (1-5): 1.
In step 2, the ratio of the volume of the aqueous phase to the volume of the organic phase is 40-50mL:30-45mL, such as 40 mL:30 mL,40 mL:35 mL,40 mL:40 mL,50 mL:45 mL,50 mL:40 mL.
The asymmetric self-supporting covalent organic framework film prepared by the invention is applied to pollutant separation.
Further, the contaminant separation includes separation of organic dyes, drug molecules, and the like.
Further, the organic dye comprises one or more of active green, rose bengal, brilliant blue, active black, congo red, indigo, methyl orange and the like; the drug molecules include one or more of tetracycline, ciprofloxacin, vitamin B12, and the like.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, an electrostatic action of the monomer and the salt is adopted to accelerate monomer mass transfer and an interfacial pre-assembly strategy interfacial polymerization method, an amine monomer is dissolved in a water phase, and then strong acid and strong alkali salt or strong acid and weak alkali salt is added to strengthen mass transfer; dissolving an aldehyde monomer in an organic phase; and then mixing the two phase solutions, and rapidly reacting the two monomers at the interface to grow into the anion, cation and neutral asymmetric covalent organic polymer film. Compared with the prior art, the interface reaction is accelerated, and the anion, cation and neutral covalent organic polymer film can be synthesized in 0.5-12 hours. For certain amine monomers and aldehyde monomers, the separation capacity obtained in the preparation of the membrane material is mainly dependent on: film formability of the film, crystallinity of the film, pore diameter of the film, and thickness of the film.
The COFs obtained by the method has an asymmetric structure, can increase gradient difference of the COFs aperture, and enhances the fluid transmission of the membrane. The preparation method is simple and convenient and controllable, and the prepared covalent organic polymer film has high crystallinity and film forming property and excellent molecular separation capability.
Drawings
FIG. 1 is a representation of TpDa-SO 3 H anion asymmetric covalent organic framework polymer membranes. (a) Upper surface SEM pictures of TpDa-SO 3 H anionic asymmetric covalent organic framework polymer film roughness; (b) SEM pictures of the smooth lower surface of TpDa-SO 3 H anion covalent organic framework polymer film; (c) SEM pictures of the upper and lower surface junctions of TpDa-SO 3 H anion asymmetric covalent organic framework polymer films; (d) Digital photographs of TpDa-SO 3 H anion asymmetric covalent organic framework polymeric membranes; (e) Schematic chemical structure of TpDa-SO 3 H anion asymmetric covalent organic framework macromolecule; (f) XRD diffraction curve of TpDa-SO 3 H anion asymmetric covalent organic framework polymer film.
FIG. 2 is a molecular separation picture of TpDa-SO 3 H anion covalent organic framework polymeric membranes, wherein the molecules include: (a) active green [ RG ]; (b) rose bengal [ RB ]; (c) brilliant blue [ BBR ]; (d) active black [ RB5]; (e) Congo Red [ CR ]; (f) methyl orange [ MO ]. The test condition is normal temperature and the pressure is 0.5MPa.
FIG. 3 is a characterization of TpPa-SO 3 H anion asymmetric covalent organic framework polymer membranes. (a) Upper surface SEM pictures of TpPa-SO 3 H anionic asymmetric covalent organic framework polymer film roughness; (b) TpPa-SO 3 H anion asymmetric covalent organic framework polymer film smooth lower surface SEM pictures; (c) SEM pictures of the upper and lower surface junctions of TpPa-SO 3 H anion asymmetric covalent organic framework polymer films; (d) Digital photographs of TpPa-SO 3 H anion asymmetric covalent organic framework polymeric membranes; (e) Schematic chemical structure of TpPa-SO 3 H anion asymmetric covalent organic framework macromolecule; (f) XRD diffraction curve of TpPa-SO 3 H anion asymmetric covalent organic framework polymer film.
FIG. 4 is a molecular separation picture of TpPa-SO 3 H anion asymmetric covalent organic framework polymeric membranes, wherein the molecules include: (a) active green [ RG ]; (b) rose bengal [ RB ]; (c) brilliant blue [ BBR ]; (d) active black [ RB5]; (e) Congo Red [ CR ]; (f) indigo [ IC ]; (g) methyl orange [ MO ]. The test condition is normal temperature and the pressure is 0.5MPa.
FIG. 5 is a characterization of TpBa-SO 3 H anion asymmetric covalent organic framework polymer membranes. (a) TpBa-SO 3 H anion covalent organic framework polymer film roughened upper surface SEM pictures; (b) TpBa-SO 3 H anion asymmetric covalent organic framework polymer film smooth lower surface SEM pictures; (c) SEM pictures of the upper and lower surface junctions of TpBa-SO 3 H anion asymmetric covalent organic framework polymer films; (d) Digital photographs of TpBa-SO 3 H anion asymmetric covalent organic framework polymeric membranes; (e) Schematic chemical structure of TpBa-SO 3 H anion asymmetric covalent organic framework macromolecule; (f) TpBa-SO 3 H anion asymmetric covalent organic framework high-power transmission electron microscope pictures of the high-molecular film.
FIG. 6 is a molecular separation picture of TpBa-SO 3 H anion asymmetric covalent organic framework polymeric membranes, wherein the molecules include: (a) active green [ RG ]; (b) rose bengal [ RB ]; (c) brilliant blue [ BBR ]; (d) active black [ RB5]. The test condition is normal temperature and the pressure is 0.5MPa.
Fig. 7 is a molecular separation picture of TpHZ cationic covalent organic framework polymeric membranes, wherein the molecules include: (a) active green [ RG ]; (b) rose bengal [ RB ]; (c) brilliant blue [ BBR ]; (d) active black [ RB5]; (e) Congo Red [ CR ]; (f) indigo [ IC ]; (g) methyl orange [ MO ]. The test condition is normal temperature and the pressure is 0.5MPa.
Fig. 8 is a molecular separation picture of TpPa neutral covalent organic framework polymeric membranes, wherein the molecules include: (a) active green [ RG ]; (b) rose bengal [ RB ]; (c) brilliant blue [ BBR ]; (d) active black [ RB5]; (e) Congo Red [ CR ]; (f) indigo [ IC ]; (g) methyl orange [ MO ]. The test condition is normal temperature and the pressure is 0.5MPa.
FIG. 9 is a photograph of drug molecule separation of TpDa-SO 3 H anion covalent organic framework polymer membranes, wherein the molecules include: (a) vitamin B12[ VB12]; (b) rifampicin [ RF ]; (c) tetracycline [ TC ]; (d) ciprofloxacin [ CF ]. The test condition is normal temperature and the pressure is 0.5MPa.
FIG. 10 shows the growth of TpPa neutral covalent organic framework polymer films at different times. (a) TpPa digital pictures of the time-varying neutral covalent organic framework polymer film; (b) TpPa (10 mmol Na 2SO4) digital pictures of the time-dependent change of neutral covalent organic framework polymer films.
FIG. 11 shows the growth of TpDt cationic covalent organic framework polymer films at different times. (a) TpDt digital pictures of the change of the cation covalent organic framework polymer film along with time; (b) TpDt (10 mmol Na 2SO4) digital pictures of the change over time of cationic covalent organic framework polymer films.
FIG. 12 is a mass transfer case in TpPa-SO 3 H anion asymmetric covalent organic framework polymer membrane system. (a) The change of absorbance of Pa-SO 3 H during interfacial transfer when Na 2SO4 is present/absent in the system; (b) When Na 2SO4 exists in the system, the absorbance changes at different time, and the transmission rate is k= 0.06075A/min; (c) When no Na 2SO4 exists in the system, the absorbance is changed at different time, and the transmission rate is k= 0.01075A/min; in the presence of Na 2SO4 in the system, the Pa-SO 3 H transfer rate is 5.7 times that of the Na 2SO4 -free transfer rate.
Detailed Description
The technical scheme of the present invention will be exemplarily described in detail with reference to specific embodiments of the present invention, but it should be understood that the scope of the present invention is not limited by the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising" and the like will be understood to include the stated elements, without excluding other elements.
Example 1: preparation of high crystallinity TpDa-SO 3 H anion type asymmetric covalent organic framework polymer film.
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3mmol of 2, 4-diaminobenzenesulfonic acid (Da-SO 3 H) and 10 mmol of sodium sulfate (strong acid strong base salt) were added to 40mL of deionized water, and the mixture was sonicated to obtain an aqueous phase mixture. The dichloromethane solution was added to an 80 mL dish, and then the aqueous phase mixture was slowly added to the organic phase solution along the circumference of the dish. Standing the culture dish at room temperature to react 12H to obtain a TpDa-SO 3 H film; and then the water and the organic solvent on the upper layer and the lower layer are sucked out by a rubber head dropper, 60mL methylene dichloride, ethanol and water are respectively added into a culture dish to be washed for 6 hours, unreacted monomers and the organic solvent are removed, and finally the membrane is placed in a deionized water phase environment for subsequent molecular separation.
The performance test of the sample of this example is shown in FIGS. 1-2. SEM images of upper and lower surfaces of the film in fig. 1 are shown as (a) - (c), (d) digital photographs of the film show excellent film forming property of TpDa-SO 3 H, (e) chemical structure of TpDa-SO 3 H, and (f) XRD proves that the prepared TpDa-SO 3 H ionic covalent organic polymer film has high crystallinity. The molecular separation is shown in figure 2, and the TpDa-SO 3 H membrane prepared has excellent molecular separation capability.
Example 2: preparation of high crystallinity TpPa-SO 3 H anionic asymmetric covalent organic framework film.
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3mmol of 2, 5-diaminobenzenesulfonic acid (Pa-SO 3 H) and 10 mmol sodium sulfate (strong acid strong base salt) were added to 40mL of deionized water, and the mixture was sonicated to obtain an aqueous phase mixed solution. The dichloromethane solution was added to an 80 mL dish, and then the aqueous phase mixture was slowly added to the organic phase solution along the circumference of the dish. Standing the culture dish at room temperature to react for 0.5H to obtain a TpPa-SO 3 H film; then the water and the organic solvent on the upper and lower layers are sucked out by a rubber head dropper, 60mL of dichloromethane, ethanol and water are respectively added into a culture dish for washing for 6 hours, unreacted monomers and organic solvent are removed, and finally the membrane is placed in a deionized water phase environment for subsequent molecular separation.
The sample performance test of this example is shown in fig. 3-4, wherein SEM images of the upper and lower surfaces of the membrane in fig. 3 are shown in (a) - (c), (d) digital photographs of the membrane show excellent film forming property of TpPa-SO 3 H, (e) chemical structure of TpPa-SO 3 H, and (f) XRD proves that the prepared TpPa-SO 3 H ionic covalent organic polymer membrane has high crystallinity. The molecular separation is shown in FIG. 4, and it can be seen that the TpPa-SO 3 H membrane prepared has excellent molecular separation capability.
Example 3: preparation of high crystallinity TpBa-SO 3 H anionic asymmetric covalent organic framework film.
Adding 2mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3 mmol of 4,4 '-diaminobiphenyl-2, 2' -disulfonic acid (Ba-SO 3 H) and 10mmol sodium sulfate (strong acid and strong alkali salt) are added into 40 mL of deionized water, and aqueous phase mixed solution is obtained by ultrasonic treatment. The dichloromethane solution was added to an 80 mL dish, and then the aqueous phase mixture was slowly added to the organic phase solution along the circumference of the dish. Standing the culture dish at room temperature for reacting for 12H to obtain TpBa-SO 3 H; and then the water and the organic solvent on the upper layer and the lower layer are sucked out by a rubber head dropper, 60 mL methylene dichloride, ethanol and water are respectively added into a culture dish to be washed for 6 hours, unreacted monomers and the organic solvent are removed, and finally the membrane is placed in a deionized water phase environment for subsequent molecular separation.
The sample performance test of this example is shown in fig. 5-6, wherein SEM images of the upper and lower surfaces of the membrane in fig. 5 are shown in (a) - (c), (d) digital photographs of the membrane show excellent film forming property of TpBa-SO 3 H, (e) chemical structure of TpBa-SO 3 H, and (f) HR-TEM show that the prepared TpBa-SO 3 H ionic covalent organic polymer membrane has high crystallinity. The molecular separation is shown in FIG. 6, and the TpBa-SO 3 H prepared has better molecular separation capability.
Example 4: comparison of film formation rates of TpPa neutral covalent organic framework polymer films prepared with Na 2SO4 (strong acid strong base salt).
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3 mmol p-phenylenediamine (Pa) and 10 mmol sodium sulfate (strong acid and strong base salt, FIG. 10 (a) no sodium sulfate, FIG. 10 (b) added sodium sulfate) were added to 40 mL deionized water, and the aqueous phase mixture was obtained by sonication. The dichloromethane solution was added to an 80 mL dish and the aqueous solution was then slowly added to the organic phase solution along the periphery of the dish. By observing the film forming conditions at different times, the comparison shows that the film forming of the neutral covalent organic framework polymer can be accelerated TpPa when sodium sulfate is added.
Example 5: comparison of film formation rates of TpDt cationic covalent organic framework polymer films prepared with Na 2SO4 (strong acid strong base salt).
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3 mmol of triaminoguanidine hydrochloride (Dt) and 10 of sodium mmol sulfate (strong acid and strong base salt, fig. 11 (a) without sodium sulfate, fig. 11 (b) with sodium sulfate) were added to 40mL of deionized water, and the aqueous phase mixture was obtained by sonication. The methylene chloride solution was added to an 80 mL dish, and then the aqueous solution was slowly added to the aqueous solution around the dish. By observing the film forming conditions at different times, the film forming of TpDt cationic covalent organic framework polymers can be accelerated by comparing with the film forming conditions at different times when sodium sulfate is added.
The mass transfer rate of Pa-SO 3 H monomer was tested, 1 mL DCM pure solvent was added in the lower layer of the dish, 3 mL aqueous solution with or without Na 2SO4 was added in the upper layer, and the mass transfer rate was tested using an ultraviolet spectrophotometer, and graphs (a), (b) in fig. 12 showed fast mass transfer rate (k= 0.06075A/min) in the presence of strong acid strong base salt (strong acid strong base salt), SO that fast film formation, and graph (c) in fig. 9 showed slow mass transfer rate (k= 0.01075A/min) in the absence of strong acid strong base salt (strong acid strong base salt), resulting in slow film formation or no film formation (table 1).
In summary, the polymerization method of the invention can provide a method for rapidly preparing the cationic, anionic and neutral covalent organic polymer film by accelerating monomer mass transfer and interfacial pre-assembly strategy provided by inorganic salt. The method has certain universality, and the prepared COFs film has the characteristics of good film forming property and high crystallinity. Wherein TpPa-SO 3 H anion covalent organic framework membrane has very excellent molecular separation capability.
Comparative example 1: attempts were made to prepare TpDa-SO 3 H anion covalent organic framework membranes without the addition of strong acid and strong base salts.
Adding 2mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3 mmol of 2, 4-diaminobenzenesulfonic acid (Da-SO 3 H) was added to 40 mL deionized water and sonicated to give an aqueous mixture. The dichloromethane solution was added to an 80 mL dish, and then the aqueous phase mixed solution was slowly added to the organic phase solution along the periphery of the dish, and the dish was left to stand at room temperature for 48: 48 h to obtain a thin film. No film can be obtained when such strong acid-free alkali salt is added.
Comparative example 2: attempts were made to prepare TpPa-SO 3 H anion covalent organic framework membranes without the addition of strong acid and strong base salts.
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3 mmol of 2, 5-diaminobenzenesulfonic acid (Pa-SO 3 H) was added to 40 mL deionized water and sonicated to obtain an aqueous phase mixture. The dichloromethane solution was added to an 80 mL dish, and then the aqueous phase mixed solution was slowly added to the organic phase solution along the periphery of the dish, and the dish was left to stand at room temperature for 1h without a membrane. When such a strong acid-free alkali salt is added, a membrane cannot be obtained, and when the reaction time is 4 h, a membrane is obtained, but such a membrane is very fragile and cannot be used for separation.
Comparative example 3: attempts were made to prepare TpBa-SO 3 H anion covalent organic framework membranes without the addition of strong acid and strong base salts.
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; 3 mmol of 4,4 '-diaminobiphenyl-2, 2' -disulfonic acid (Ba-SO 3 H) was added to 40mL of deionized water and sonicated to obtain an aqueous phase mixture. The dichloromethane solution was added to an 80 mL dish, and then the aqueous phase mixed solution was slowly added to the organic phase solution along the periphery of the dish, and the dish was left to stand at room temperature for 3 months without a film. No film can be obtained when such strong acid-free alkali salt is added.
Comparative example 4: attempts were made to prepare TpPa-SO 3 H anion covalent organic framework membranes when weak acid strong base salts (e.g., sodium bicarbonate, sodium phosphate, etc.) were added.
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; adding 3 mmol-2, 5-diaminobenzenesulfonic acid (Pa-SO 3 H) and 10 mmol weak acid strong alkali salt (such as sodium bicarbonate, sodium phosphate or the like) into 40 mL deionized water, and performing ultrasonic treatment to obtain water phase mixed solution. The dichloromethane solution was added to an 80 mL dish, and then the aqueous phase mixed solution was slowly added to the organic phase solution along the periphery of the dish, and the dish was left to stand at room temperature for 30 days without a film. When such a weak acid and strong alkali salt is added, a film cannot be obtained.
Comparative example 5: attempts were made to prepare TpPa-SO 3 H anion covalent organic framework films when adding different metal cation sulfates (e.g., magnesium sulfate, iron sulfate, etc.).
Adding 2 mmol trialdehyde phloroglucinol into a dichloromethane organic phase solution, and performing ultrasonic treatment to obtain a clear solution; any one of 3 mmol-2, 5-diaminobenzenesulfonic acid (Pa-SO 3 H) and 10 mmol magnesium sulfate or ferric sulfate is added into 40mL deionized water, and the water phase mixed solution is obtained by ultrasonic treatment. The dichloromethane solution was added to an 80mL dish, and then the aqueous phase mixed solution was slowly added to the organic phase solution along the periphery of the dish, and the dish was left to stand at room temperature for 5 days. In this case TpPa-SO 3 H anion covalent organic framework films were not obtained.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (5)
1. The preparation method of the asymmetric self-supporting covalent organic framework film is characterized by comprising the following steps of:
Step 1: respectively dissolving an amine monomer and inorganic salt in an aqueous solution, and then mixing the two to obtain an aqueous solution, wherein the inorganic salt provides a driving force to promote the amine monomer to accelerate mass transfer; dissolving polybasic aldehyde in a solvent dichloromethane to obtain an organic phase solution;
Step 2: adding an organic phase solution into the reactor, slowly adding the aqueous phase solution above the organic phase solution along the edge of the reactor, and standing at room temperature for reaction for 0.5-12 hours;
step 3: sucking water and dichloromethane solution in the reaction system, sequentially adding dichloromethane, ethanol and water solution to wash out excessive monomers and salt, and then placing the membrane in water to obtain an ionic or neutral covalent organic framework polymer membrane;
The amine monomer is selected from the group consisting of 2, 5-diaminobenzenesulfonic acid, 2, 4-diaminobenzenesulfonic acid, 4' -diaminobiphenyl-2, 2' -dicarboxylic acid, 4' -diaminobiphenyl-2, 2' -disulfonic acid, 4' -diamino-1, 1' -biphenyl-3, 3' -dicarboxylic acid, p-phenylenediamine, 4' -biphenyldiamine, 3, 5-diamino-1, 2, 4-triazole, 9H-carbazole-3, 6-diamine, 4' -azobis-aniline one of 1,3, 5-tris (4-aminophenyl) benzene, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, tris (4-aminophenyl) amine, trans-1, 4-cyclohexanediamine, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9-bis (4-aminophenyl) fluorene, ethidium bromide, tris aminoguanidine hydrochloride, hydrazine hydrate, tris (2-aminoethyl) amine;
The inorganic salt is a strong acid and strong alkali salt or a strong acid and weak alkali salt, the strong acid and strong alkali salt is selected from one or more of Na 2SO4、NaCl、NaNO3, and the strong acid and weak alkali salt is selected from one or more of (NH 4)2SO4、NH4NO3、NH4 Cl).
2. The method of manufacturing according to claim 1, characterized in that:
The polyaldehyde is selected from the group consisting of triallylbenzenes, trimellitic aldehyde, thieno [3,2-b ] thiophene-2, 5-dicarboxaldehyde, 2-hydroxy-1, 3, 5-benzene tricaldehyde, 2-hydroxybenzene-1, 4-dicarboxaldehyde, 2, 5-difluoro terephthalaldehyde, 2, 5-dimethoxy benzene-1, 4-dicarboxaldehyde, 2, 5-dichloro terephthalaldehyde, 2, 5-dibromobenzene-1, 4-dicarboxaldehyde, 2, 5-dimethyl terephthalaldehyde, tetrafluoroterephthalaldehyde, 5,10,15, 20-tetrakis (4-aldyl benzene) -21H, 23H-porphyrin, 4 '-biphenyl dicarboxaldehyde, 2, 5-dihydroxy-1, 4-benzene dicarboxaldehyde, 2-bipyridine-4, 4-dicarboxaldehyde, 1,2,4, 5-tetrakis (4-formylphenyl) benzene, 4' - (2, 2-bis 4-formylphenoxy) methyl) propane-3-diyl) bis (oxy)) of the dialdehyde.
3. The method of manufacturing according to claim 1, characterized in that:
In the step 1, the molar concentration of inorganic salt in the aqueous phase solution is 1-10mmol/L, and the molar concentration of amine monomer is 0.1-9 mmol/L; the molar concentration of the polyaldehyde monomer in the organic phase solution is 0.1-9 mmol/L.
4. Use of an asymmetric self-supporting covalent organic framework film prepared according to the method of any one of claims 1-3 for contaminant separation.
5. The use according to claim 4, characterized in that:
the pollutant separation comprises separation of organic dye and drug molecules;
The organic dye comprises one or more of active green, rose bengal, brilliant blue, active black, congo red, indigo and methyl orange; the drug molecules include one or more of tetracycline, ciprofloxacin and vitamin B12.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110605098A (en) * | 2019-09-30 | 2019-12-24 | 江南大学 | Non-reversible covalent organic framework for efficiently and selectively recovering gold and preparation method thereof |
| CN111647184A (en) * | 2020-06-28 | 2020-09-11 | 闽江学院 | Covalent organic framework film material for removing triclosan in environmental water and preparation method and application thereof |
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| CN112321782B (en) * | 2020-10-19 | 2021-12-03 | 华中科技大学 | Crystalline covalent triazine organic framework material and preparation method and application thereof |
| CN112321839B (en) * | 2020-10-30 | 2022-02-22 | 郑州轻工业大学 | Bimetal covalent organic framework material, preparation method thereof and aptamer sensor |
| CN112679731B (en) * | 2020-12-21 | 2022-08-23 | 同济大学 | Covalent organic framework material containing sulfonic acid group and preparation and application thereof |
| CN113372523B (en) * | 2021-04-02 | 2023-08-29 | 同济大学 | Transition metal ion modified sulfonic acid covalent organic framework material and preparation and application thereof |
| CN113461933B (en) * | 2021-06-01 | 2022-09-06 | 浙江大学 | Polymer self-supporting nano film, continuous and macro preparation method and application thereof |
| CN113621118B (en) * | 2021-07-08 | 2024-10-29 | 南京理工大学 | Alkyl chain modified covalent organic framework film, preparation method and application thereof |
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| CN114456338B (en) * | 2021-12-24 | 2023-03-14 | 江南大学 | Photocatalytic synthesis method of benzimidazolyl covalent organic framework material |
| CN114456339B (en) * | 2022-02-11 | 2023-06-27 | 天津大学浙江研究院 | Covalent organic framework film with high ionic group content, preparation method and application thereof |
| WO2024015937A2 (en) * | 2022-07-13 | 2024-01-18 | Northwestern University | Covalent organic frameworks for gas chromatographic separations |
| CN115178109B (en) * | 2022-08-01 | 2023-08-15 | 同济大学 | Composite nanofiltration membrane based on covalent organic framework compound NCOF and preparation method thereof |
| CN115814601A (en) * | 2022-10-31 | 2023-03-21 | 浙江大学 | Preparation method and application of ionic covalent organic framework membrane material |
| CN115850625A (en) * | 2022-11-04 | 2023-03-28 | 南京工业大学 | Preparation method of covalent organic framework and application of covalent organic framework in photocatalytic seawater hydrogen evolution |
| CN115947911B (en) * | 2023-02-28 | 2023-05-23 | 天津大学 | Diketimine-linked covalent organic framework polymer material and preparation method thereof |
| CN117482758A (en) * | 2023-10-30 | 2024-02-02 | 东北林业大学 | Ionic covalent organic framework composite membrane, preparation method and application thereof in separating dye and salt |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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