CN111686807B - Intelligent catalytic membrane constructed based on stimulus-responsive microgel and preparation method and application thereof - Google Patents
Intelligent catalytic membrane constructed based on stimulus-responsive microgel and preparation method and application thereof Download PDFInfo
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- CN111686807B CN111686807B CN202010547898.XA CN202010547898A CN111686807B CN 111686807 B CN111686807 B CN 111686807B CN 202010547898 A CN202010547898 A CN 202010547898A CN 111686807 B CN111686807 B CN 111686807B
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- microgel
- membrane
- catalytic
- sodium
- metal
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- 239000012528 membrane Substances 0.000 title claims abstract description 138
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000002184 metal Substances 0.000 claims abstract description 59
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 230000008961 swelling Effects 0.000 claims abstract description 6
- 230000002441 reversible effect Effects 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 15
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 238000003756 stirring Methods 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
- HMLSBRLVTDLLOI-UHFFFAOYSA-N 1-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)C(C)OC(=O)C(C)=C HMLSBRLVTDLLOI-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- OWHUYYOLMQBAHA-UHFFFAOYSA-M sodium octadecanoate prop-2-enamide Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Na+].C(C=C)(=O)N OWHUYYOLMQBAHA-UHFFFAOYSA-M 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract description 2
- 230000000638 stimulation Effects 0.000 abstract description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 13
- 239000002082 metal nanoparticle Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000000614 phase inversion technique Methods 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- AYKOTYRPPUMHMT-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag] AYKOTYRPPUMHMT-UHFFFAOYSA-N 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The application discloses an intelligent catalytic membrane constructed based on stimulus-responsive microgel and a preparation method and application thereof, wherein the preparation method of the intelligent catalytic membrane is as follows: (1) Preparing a stimulus-responsive microgel having reversible swelling/shrinking properties; (2) Adding a metal salt solution into the microgel dispersion liquid, and preparing nano metal loaded composite microgel by an in-situ reduction method; (3) Dispersing the composite microgel in deionized water to form dispersion liquid, regulating the pH value of the dispersion liquid to 2-5, and filling the composite microgel in the dispersion liquid into a microporous filter membrane in a dynamic filtration mode; (4) And (3) adjusting proper stimulation conditions to enable the composite microgel to be swelled and firmly embedded in the microporous filter membrane, so as to prepare the intelligent catalytic membrane immobilized with the composite microgel. The intelligent catalytic membrane prepared by the invention has the characteristics of stable structure, high catalytic efficiency, reusability and the like, and can effectively solve the technical problem of high-efficiency load of the noble metal nano catalyst.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to an intelligent catalytic membrane constructed based on stimulus-responsive microgel, and a preparation method and application thereof.
Background
The metal nano particles have small particle size, large specific surface area and high catalytic efficiency, so that the metal nano particles are widely applied in the catalytic field. However, the direct use of metal nanoparticles presents serious challenges. First, due to the large surface energy of the nanoparticles, metal nanoparticles tend to agglomerate in liquids, decreasing their effective surface area and increasing the average particle size, which is often greatly affected in catalytic stability and reproducibility (see Zhao M, sun L, crooks R m. Preparation of Cu Nanoclusters within Dendrimer Templates [ J ]. Journal of the American Chemical Society, 1998, 120 (19): 4877-4878.). Secondly, the separation and recovery of the nanoparticles after the end of the reaction is cumbersome and expensive. This has made it inadequate for green chemistry and sustainable development.
The selection of a proper carrier for the loading of nano metal is an important means for preventing agglomeration of metal nano particles and improving the catalytic activity of the catalyst. At present, common nano-metal particle carriers mainly comprise metal oxides, non-metal oxides, C-based carriers, polymers and the like. For example, chinese patent CN109126784A discloses a metal nanoparticle/silicon dioxide composite catalyst, a preparation method and application thereof, wherein the method adopts 3-aminopropyl triethoxysilane to prepare the spherical SiO 2 And (3) modifying, and then compositing the modified catalyst with metal nano particles to prepare the composite catalyst. However, due to SiO 2 The small size of the microspheres (300-600 nm), easy agglomeration, and difficult use and reuse of the catalyst. Chinese patent CN104084189a discloses an activated carbon catalyst loaded with nano metal particles and a preparation method thereof, and although the method is easy to recover, the nano metal catalytic efficiency inside the activated carbon is reduced due to the large mass transfer resistance. Chinese patent CN105536869A discloses a preparation method of a nano-silver loaded hybrid microgel catalyst, wherein the hybrid microgel is prepared from PNIPAM microgel and nano-particles on the surface of the PNIPAM microgelThe silver particles form, the nano silver can be stably dispersed in the gel, the aggregation of the nano silver is avoided, and the catalyst stability is good. However, the microgel still cannot avoid the problems of difficult recovery and easy loss in the use process.
The high molecular polymer membrane can effectively pass through the micro-channel of the high molecular polymer membrane due to high porosity and micro-nano pore size distribution, and the porous structure also provides possibility for nanoparticle loading, so that the catalytic membrane loaded with nano metal is expected to be constructed into a novel membrane reactor taking the catalytic membrane as a core component. The existing preparation methods of the catalytic membrane mainly comprise the following steps: (1) The noble metal nano particles are adsorbed and deposited on the surface of the polymer film, and the catalyst is only fixed on the surface of the film, so that the utilization rate of the catalyst and the film base material is low, and the stability of the catalyst is poor, so that the catalytic film prepared by the method has low catalytic rate and is easy to cause loss of the catalyst. Chinese patent CN102512991a discloses a catalytic membrane prepared based on layer-by-layer self-assembly technology and containing metal palladium active functional layer and its preparation method. The surface of the polyacrylonitrile membrane is alternately immersed in a solution containing polyethyleneimine-palladium coordination compound and a sodium polystyrene sulfonate solution to self-assemble a functional layer on the surface of the membrane, and then the functional layer with palladium nano metal is generated by in-situ reduction. Although the method can obtain the catalytic functional layer with controllable metal content on the surface of the membrane, a large number of micro-channel structures in the membrane substrate are not fully utilized, so that the catalytic efficiency is not high. (2) And adding a catalyst in the preparation process of the polymer membrane to obtain the catalytic membrane. The catalyst added corresponds to the additive added during membrane preparation, but often affects the catalytic activity due to entrapment in the membrane material or uneven distribution in the membrane. Chinese patent CN104984668A adopts a thermal phase inversion method to prepare a nano particle doped polyvinylidene fluoride catalytic membrane, and the nano particles are easy to agglomerate to cause uneven dispersion, so that the membrane performance is reduced, the strength is low, and the practical application is limited. Chinese patent CN107118477a discloses a carbon coated metal nanoparticle loaded PVDF membrane and a method for preparing the same. And mixing the synthesized carbon-coated metal nano particles with PVDF powder, organic additives and the like, and preparing the catalytic film by a phase inversion method. The catalyst used as the additive of the casting solution has great influence on the film structure and performance, and has a narrow application range. Chinese patent CN108479412a mixes temperature responsive microsphere carrying nano metal catalyst with polyethersulfone powder, additive, etc., and prepares catalytic film by phase inversion method. The membrane pore structure can be changed along with the different addition amounts of the hybrid polymer microspheres, and the polymer microspheres are easy to be embedded by a membrane substrate, so that the catalytic efficiency of the catalyst is reduced.
Compared with the conventional preparation method of the catalytic membrane, the catalytic membrane prepared by dynamically filtering nano metal/environmental response microgel on the microporous filter membrane has a few reports, the catalytic performance of the catalytic membrane can be changed according to the change of external treatment working conditions, and a good catalytic effect is maintained. The catalytic membrane has the characteristics of stable structure, high catalytic efficiency, low transmembrane resistance, reusability and the like, can be used for high-efficiency load of noble metal nano catalysts, enhances the reaction efficiency through the flow limiting principle, can realize effective recovery of non-renewable resources, and provides a wider application prospect in the catalytic membrane field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an intelligent catalytic membrane constructed based on stimulus-responsive microgel, a preparation method and application thereof, and the invention can effectively utilize the characteristics of high porosity and micro-nano pore diameter distribution of a membrane substrate, realize the effective load of a noble metal nano catalyst by immobilizing nano metal/microgel into a membrane pore through a dynamic filtration method, and realize the continuous treatment of p-nitrophenol through constructing a flow-through reactor.
The nano metal/microgel catalytic membrane provided by the invention consists of a microporous filter membrane substrate and composite microgels which are distributed in the membrane substrate and carry nano metal catalysts. The composite microgel loaded with the nano metal catalyst is an environment response microgel prepared by free radical polymerization of a monomer a and a monomer b, and is composed of nano metal fixed in a microgel crosslinked network structure by in-situ reduction. In the nano metal/microgel catalytic membrane provided by the invention, composite microgels are mainly distributed on the surface of a membrane substrate and in pore channels; the flux and catalytic performance of the catalytic membrane change along with the change of external environmental conditions, and the catalytic efficiency can be improved.
The intelligent catalytic membrane is prepared by the following steps: (1) Preparing a stimulus-responsive microgel having reversible swelling/shrinking properties; (2) Adding a metal salt solution into the microgel dispersion liquid, and preparing nano metal loaded composite microgel by an in-situ reduction method; (3) Dispersing the composite microgel in deionized water to form dispersion liquid, regulating the pH value of the dispersion liquid to 2-5, and filling the composite microgel in the dispersion liquid into a microporous filter membrane in a dynamic filtration mode; (4) And (3) adjusting proper stimulation conditions to enable the composite microgel to be swelled and firmly embedded in the microporous filter membrane, so as to prepare the intelligent catalytic membrane immobilized with the composite microgel.
Specifically, the technical scheme of the invention is as follows:
a method for constructing an intelligent catalytic membrane based on stimulus-responsive microgel is prepared by the following steps:
1) Adding a monomer a, a monomer b, a cross-linking agent, an initiator, a surface active substance and a solvent into a polymerization reactor, and uniformly mixing and dispersing; under the protection of nitrogen, slowly heating to 60-80 ℃ for reaction for 2-8 hours, cooling to room temperature, centrifuging, and freeze-drying to obtain microgel with reversible swelling-shrinking property;
the monomer a is at least one of acrylamide, N-isopropyl acrylamide, N-dimethylamino ethyl methacrylate, N-vinyl caprolactam, N-methylolacrylamide, diacetone acrylamide, N-dimethyl acrylamide and N-tertiary butyl acrylamide; the monomer b is one of acrylic acid and methacrylic acid.
The cross-linking agent is N, N-methylene bisacrylamide; the initiator is one of potassium persulfate, ammonium persulfate, azodiisobutylamidine hydrochloride, sodium persulfate, azodiiso Ding Mi hydrochloride, azodicyanovaleric acid and azodiisopropyl imidazoline hydrochloride; the surface active substance is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium oleate, potassium oleate, sodium p-styrenesulfonate, acrylamide sodium stearate, sodium allyl succinate alkyl sulfonate, dodecyl ammonium chloride and hexadecyl trimethyl ammonium bromide; the solvent is water.
The ratio of the amounts of the monomers a, b, crosslinking agent, initiator and surface active substance is 1:0.1-9:0.02-0.8:0.02-0.4:0.002-0.04, particularly preferably 1:0.5:0.14:0.1:0.01; the mass ratio of the monomer a to the solvent is from 1:140 to 420, particularly preferably 1:300.
2) Dispersing the microgel obtained in the step 1) in deionized water, adding an aqueous solution containing metal catalyst ions, and mechanically stirring for 1-6 hours at room temperature; then slowly dripping a reducing agent solution under the protection of nitrogen, and continuously reacting for 4-8 hours, wherein the reducing agent reduces the metal catalyst ions loaded on the microgel into nano metal simple substances in situ; after the reaction is finished, the nano metal loaded composite microgel is obtained through centrifugation, dialysis and freeze drying and is marked as nano metal/microgel material.
The aqueous solution containing metal catalyst ions is prepared by dissolving water-soluble salts and water, wherein the water-soluble salts comprise at least one of water-soluble copper salt, water-soluble ruthenium salt, water-soluble cobalt salt, water-soluble nickel salt, water-soluble gold salt, water-soluble palladium salt, water-soluble silver salt and water-soluble platinum salt; the reducing agent is one of sodium borohydride, sodium citrate, hydrazine hydrate and ascorbic acid, and sodium borohydride is particularly preferred.
The microgel is dispersed in deionized water, and the mass concentration of the formed microgel dispersion is 0.05-0.15%, and particularly preferably 0.1%. The molar concentration of the aqueous solution containing metal catalyst ions is from 0.5 to 2 mM, particularly preferably 1 mM. The molar ratio of the reducing agent to the metal catalyst ions is 15-40:1, preferably 20:1.
3) Dispersing the nano metal/microgel material obtained in the step 2) in deionized water, and regulating the pH of the formed dispersion liquid to 2-5 by using hydrochloric acid; uniformly filling nano metal/microgel materials in the dispersion liquid onto a microporous filter membrane serving as a framework material by a dynamic filtration method, namely carrying out suction filtration on the composite microgel dispersion liquid by adopting the microporous filter membrane of the framework material; washing the surface of the membrane with deionized water after the suction filtration is completed, so as to obtain a treated membrane;
the microporous filter membrane comprises one of, but not limited to, a polypropylene membrane, a polyamide membrane, a polyether sulfone membrane, a cellulose acetate membrane, a nitrocellulose membrane, a polysulfone membrane, a polyvinylidene fluoride membrane, a polytetrafluoroethylene membrane and the like, and the pore size distribution range of the microporous filter membrane is 0.2-5 mu m.
4) And 3) fixing the membrane obtained in the step 3) on a filtering device, filtering by using a sodium hydroxide aqueous solution with the pH value of 9-12, swelling the nano metal/microgel material and firmly embedding the nano metal/microgel material into a microporous filter membrane, thus obtaining the intelligent catalytic membrane product immobilized with the nano metal/microgel material.
The invention also provides an application of the intelligent catalytic membrane prepared by the method in catalytic reduction treatment of p-nitrophenol.
Because the intelligent catalytic membrane immobilized with the nano metal/microgel material provided by the invention has flux and catalytic performance which change along with the change of response environmental conditions. Based on the method, when the intelligent catalytic film provided by the invention is used for treating the p-nitrophenol, as sodium borohydride is used as a reducing agent and a reaction system is used as an alkali environment, the nano metal/microgel material in the catalytic film swells, so that the improvement of the catalytic performance of the catalytic film is facilitated, and the efficient catalysis is realized. Specifically, the reaction liquid system was passed through a reaction apparatus (a catalytic membrane was fixed to a filtration apparatus as a reaction apparatus) in a continuous flow mode by a peristaltic pump, and effluent was collected, and the conversion of p-nitrophenol was calculated by liquid chromatography to evaluate the catalytic performance.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is to fix the environment response microgel loaded with nano metal catalyst into the film base material on the market. In the preparation process of the environment-responsive microgel loaded with the nano metal catalyst, the nano metal simple substance serving as the active ingredient of the catalyst is fixed in a cross-linked network structure of the microgel polymer through in-situ reduction, the fixing mode of the nano metal simple substance is simple, and the nano metal simple substance has good dispersibility and stability on the microgel, so that the reusability and stability of the catalytic membrane are improved. And secondly, the environment-responsive microgel loaded with the nano metal catalyst is mainly distributed on the surface and in the pore canal of the membrane substrate, so that the high-efficiency load of the noble metal nano catalyst is realized, the effective utilization rate of the catalytic membrane is improved, and the catalytic efficiency of the catalytic membrane is improved.
2. According to the intelligent catalytic membrane immobilized with the nano metal/microgel material, a large number of environment-responsive microgels loaded with the nano metal catalysts are distributed in the membrane substrate, the particle size of the environment-responsive microgels loaded with the nano metal catalysts can be changed along with the change of environmental conditions, and the flux and catalytic performance of the catalytic membrane are also changed along with the change of environmental conditions. When the intelligent catalytic membrane is used for carrying out continuous catalytic treatment on a reaction liquid system, through reasonably adjusting the environmental conditions (namely reasonably adjusting the pH value of the reaction liquid system), the composite microgel can be swelled and the particle size is increased, so that more nano metal catalysts loaded on the microgel are exposed on the surface of the composite microgel, the catalytic efficiency of the intelligent catalytic membrane is improved, and the catalytic efficiency of the membrane can be further effectively improved through the principle of limiting flow.
3. The preparation method of the intelligent catalytic membrane provided by the invention has no special requirements on equipment and raw materials, is suitable for various commercially available microporous filter membranes, can load various nano metals, is easy to meet the conditions of environmental temperature and the like in the reaction process, is simple and convenient, is high-efficient, has lower cost, and is easy to realize industrialization.
4. The intelligent catalytic membrane prepared by the invention can be constructed into a flow-through reactor, so that continuous treatment of reactants is realized, the traditional filtration and centrifugation means are avoided when the catalyst is subjected to aftertreatment, and the catalytic and separation green reaction is realized at one time. The catalytic film and the preparation method thereof not only solve the problems of difficult dispersion, easy loss and the like of the noble metal nano catalyst, but also can effectively improve the catalytic efficiency, and have great potential in industrial production and application.
Drawings
FIG. 1a is a transmission electron microscope image of the microgel of example 1;
FIG. 1b is a transmission electron microscope image of the Ag nanoparticle-loaded composite microgel of example 1;
FIG. 2a is a cross-sectional scanning electron microscope image of a blank polysulfone microporous filter membrane of example 1;
FIG. 2b is a cross-sectional scanning electron microscope image of the polysulfone microporous filter membrane immobilized with the composite microgel of example 1;
FIG. 3 is an EDS diagram of a polysulfone microporous filter membrane immobilized with a composite microgel in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
The preparation of the intelligent catalytic membrane in this example is carried out according to the following steps:
(1) 2.23 g of N-vinyl caprolactam, 0.756g of acrylic acid, 0.219, g of N, N-methylene bisacrylamide, 0.078, g of potassium persulfate, 0.0124, g of sodium dodecyl sulfate and 300, g of solvent water are added into a 500mL three-neck flask, and the mixture is uniformly dispersed; under the protection of nitrogen, the mixture is put into a constant temperature oil bath pot with the temperature of 70 ℃ for heating reaction for 4 hours, cooled to room temperature, centrifuged and freeze-dried to obtain the microgel.
(2) Weighing the microgel 100 mg obtained in the step (1), dispersing in 200 mL deionized water, adding 50 mL of 1 mM silver nitrate aqueous solution, and mechanically stirring at room temperature for 4 hours; then under the protection of nitrogen, 40 mL of 20 mM sodium borohydride solution is slowly added dropwise, and the reaction is continued for 4 hours; after the reaction is finished, obtaining the nano Ag-loaded composite microgel through centrifugation, dialysis and freeze drying;
(3) Weighing the composite microgel obtained in the step (2), dispersing in deionized water, wherein the mass concentration of the microgel dispersion liquid is 0.001%, and regulating the pH value of the dispersion liquid to 3 by using hydrochloric acid; uniformly suction-filtering the 500mL composite microgel dispersion liquid on a polysulfone microporous filter membrane, wherein the effective filtering area is 12.56 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Washing the surface of the membrane with deionized water after the suction filtration is completed, and obtaining a treated membrane;
(4) And (3) fixing the membrane obtained in the step (3) on a filtering device, filtering by using NaOH aqueous solution with pH value of 9-12, swelling the composite microgel and firmly embedding the composite microgel in a microporous filter membrane, thus obtaining the intelligent catalytic membrane.
Fig. 1a is a transmission electron microscope image of the microgel prepared in step (1) of example 1, and fig. 1b is a transmission electron microscope image of the Ag nanoparticle-loaded composite microgel prepared in step (2). By comparing the fig. 1a and 1b, it can be clearly seen that many Ag nanoparticles are distributed on the surface and inside of the composite microgel, and the average size of the Ag nanoparticles is about 7nm, which also indicates that the method successfully synthesizes the composite microgel loaded with Ag nanoparticles.
FIG. 2a is a cross-sectional scanning electron microscope image of a blank commercially available polysulfone microporous filter membrane in example 1, and FIG. 2b is a cross-sectional scanning electron microscope image of a polysulfone microporous filter membrane immobilized with a composite microgel prepared in step (3) in example 1. By comparing fig. 2a and fig. 2b, it is evident that a large amount of composite microgel is distributed in the internal channels of the microporous filter membrane, which also demonstrates that the present method successfully immobilizes the composite microgel on the microporous filter membrane on the market.
FIG. 3 is an EDS chart of the microporous membrane immobilized with the composite microgel prepared in the step (3) of example 1, and the detection result shows that Ag element is indeed present on the membrane.
Example 2
The smart catalytic membrane of example 2 was prepared as follows:
(1) 2.23 g of N-vinyl caprolactam, 0.756g of acrylic acid, 0.219, g of N, N-methylene bisacrylamide, 0.078, g of potassium persulfate, 0.0124, g of sodium dodecyl sulfate and 300, g of solvent water are added into a 500mL three-neck flask, and the mixture is uniformly dispersed; under the protection of nitrogen, the mixture is put into a constant temperature oil bath pot with the temperature of 70 ℃ for heating reaction for 4 hours, cooled to room temperature, centrifuged and freeze-dried to obtain the microgel.
(2) Weighing the microgel obtained in the step (1), dispersing in deionized water, wherein the mass concentration of the microgel dispersion liquid is 0.001%, and regulating the pH value of the dispersion liquid to 3 by using hydrochloric acid; uniformly suction-filtering 500mL microgel dispersion liquid on polysulfone microporous filter membrane, and its effective filtering area is 12.56 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Washing the surface of the membrane with deionized water after the suction filtration is completed, and obtainingA treated film;
(3) And (3) fixing the membrane obtained in the step (2) on a filtering device, filtering by using NaOH aqueous solution with pH value of 9-12, swelling the microgel and firmly embedding the microgel in a microporous filter membrane, thus obtaining the intelligent catalytic membrane.
It can be seen that the preparation step of the smart catalytic film of example 2 is different from example 1 only in that "the preparation process without nano Ag supported in example 2" and other steps and parameters are the same as example 1.
Example 3
The procedure for preparing the smart catalytic membrane of example 3 was repeated for example 1, except that the volume of the composite microgel dispersion suction filtered in step (3) of example 1 was changed from 500mL to 100mL, and the other steps and parameters were the same as in example 1.
Example 4
The procedure for preparing the smart catalytic membrane of example 4 was repeated for example 1, except that "1 mM silver nitrate aqueous solution in step (2) of example 1 was replaced with an equivalent molar concentration of platinum chloride aqueous solution", and the other steps and parameters were the same as in example 1.
Example 5
The procedure for preparing the smart catalytic membrane of example 5 was repeated for example 1, except that "1 mM silver nitrate aqueous solution in step (2) of example 1 was replaced with an equal molar concentration palladium chloride aqueous solution", and other steps and parameters were the same as in example 1.
Example 6
The procedure for preparing the smart catalytic membrane of example 6 was repeated for example 1, except that "1 mM aqueous silver nitrate solution in step (2) of example 1 was replaced with an aqueous gold chloride solution of the same molar concentration", and the other steps and parameters were the same as those of example 1.
Example 7
The procedure for preparing the smart catalytic membrane of example 7 was repeated for example 1, except that "1 mM silver nitrate aqueous solution in step (2) of example 1 was replaced with nickel chloride aqueous solution of the same molar concentration", and other steps and parameters were the same as those of example 1.
Example 8
The procedure for preparing the smart catalytic membrane of example 8 was repeated for example 1, except that "1 mM silver nitrate aqueous solution in step (2) of example 1 was replaced with cobalt chloride aqueous solution of the same molar concentration", and other steps and parameters were the same as those of example 1.
Example 9
The procedure for preparing the smart catalytic membrane of example 9 was repeated for example 1, except that "1 mM silver nitrate aqueous solution in step (2) of example 1 was replaced with an equivalent molar concentration of copper chloride aqueous solution", and other steps and parameters were the same as those of example 1.
Example 10
The procedure for preparing the smart catalytic membrane of example 10 was repeated for example 1, except that "1 mM silver nitrate aqueous solution in step (2) of example 1 was replaced with ruthenium chloride aqueous solution of the same molar concentration", and other steps and parameters were the same as in example 1.
Application example 11
Catalytic performance test of catalytic membrane:
in the application example, sodium borohydride is used for reducing paranitrophenol as a model reaction to illustrate the application effect of the prepared catalytic film in catalytic treatment, and the conversion rate of the paranitrophenol is mainly examined.
The transmembrane catalytic test was carried out by using a flow-through reaction apparatus (i.e., a filtration apparatus), the catalytic membranes prepared in examples 1 to 10 were each cut to a suitable size and fixed on the filtration apparatus, and the reaction solution (the concentration of p-nitrophenol substance in the liquid storage tank was 1.4X10 -4 The mass concentration of M, sodium borohydride was 0.15, M, the solvent was water) was flowed through the reaction apparatus in a continuous flow mode by a peristaltic pump, and the residence time of the reaction solution on the catalytic membrane was controlled to 2 seconds by adjusting the rotational speed of the peristaltic pump. After 2 hours of the stabilization experiment, the effluent was collected, and the conversion of p-nitrophenol was calculated by liquid chromatography to evaluate the catalytic performance with the conversion of p-nitrophenol. When the catalytic membranes prepared in examples 1-10 were used in the catalytic reaction of p-nitrophenolThe conversion results are shown in Table 1.
From table 1, comparative example 1 and example 2, it can be seen that excellent catalytic performance was exhibited when the catalytic film was immobilized with the composite microgel containing Ag nanoparticles, whereas the catalytic film was completely devoid of catalytic activity when the microgel not immobilized with Ag nanoparticles, which further confirmed that the Ag nanocatalyst was stably supported on the film.
From table 1, comparative example 1 and example 3, it can be seen that the catalytic performance of the catalytic membrane increases with increasing loading of the composite microgel, since more composite microgels will provide more catalytically active sites, which is beneficial for increasing the reaction rate. As can be seen from comparative examples 4-10, the process of the present invention is applicable to many nanometals and different nanometals have different catalytic activities, which also demonstrates the versatility of the process.
In the flow-through reaction apparatus in which the catalytic film was assembled in example 1, the reaction solution (the concentration of p-nitrophenol substance in the reaction solution was 1.4X10) -4 M, sodium borohydride substance with the mass concentration of 0.15 and M, and water as solvent) continuously flows through the flow-through reaction device to perform continuous catalytic reduction treatment on the nitrophenol. The effluent from the experiment for 10 hours was collected, and the conversion of p-nitrophenol was calculated by liquid chromatography, and the results are shown in Table 2.
From table 2, the catalytic effect of the catalytic film used continuously was compared, and when the catalytic film remained to maintain good catalytic performance after continuous use of 10 a h a, this confirmed that the catalytic film had excellent stability, the nanocatalyst was effectively immobilized in the film, and the catalytic performance was maintained stable, and the conditions of continuous use could be satisfied.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (7)
1. The method for constructing the intelligent catalytic membrane based on the stimulus-responsive microgel is characterized by comprising the following steps of:
1) Dispersing the microgel with reversible swelling-shrinking property in deionized water, adding an aqueous solution containing metal catalyst ions, and mechanically stirring for 1-6 hours at room temperature; then under the protection of nitrogen, dropwise and slowly adding a reducing agent solution, and continuing to react for 4-8 hours, wherein the reducing agent reduces metal catalyst ions loaded on the microgel into nano metal simple substances in situ; after the reaction is finished, obtaining nano metal loaded composite microgel through centrifugation, dialysis and freeze drying, and marking the composite microgel as nano metal/microgel material;
2) Dispersing the nano metal/microgel material obtained in the step 1) in deionized water, adding acid into the formed dispersion liquid to adjust the pH to 2-5, and then enabling the dispersion liquid to flow through a microporous filter membrane by a dynamic filtration method so as to uniformly load the nano metal/microgel material onto the microporous filter membrane serving as a framework material; washing the membrane surface of the microporous filter membrane with deionized water after the filtration is completed to obtain a treated microporous filter membrane;
3) Fixing the microporous membrane treated in the step 3) on a filtering device, filtering by alkali liquor with pH value of 9-12, and swelling the nano metal/microgel material to firmly inlay the nano metal/microgel material in the microporous membrane serving as a framework material, thus obtaining an intelligent catalytic membrane product immobilized with the nano metal/microgel material;
in the step 1), the aqueous solution containing metal catalyst ions is prepared by dissolving water-soluble metal salt in water, wherein the metal salt is at least one of copper salt, ruthenium salt, cobalt salt, gold salt, palladium salt, silver salt and platinum salt; the reducing agent is one of sodium borohydride, sodium citrate, hydrazine hydrate and ascorbic acid;
in the step 1), the preparation method of the microgel with reversible swelling-shrinking property comprises the following steps: adding a monomer a, a monomer b, a cross-linking agent, an initiator, a surface active substance and a solvent into a polymerization reactor, and uniformly mixing and dispersing; under the protection of nitrogen, heating to 60-80 ℃ for reaction for 2-8 hours, cooling to room temperature, centrifuging, and freeze-drying to obtain the microgel;
the monomer a is at least one of acrylamide, N-isopropyl acrylamide, N-dimethylamino ethyl methacrylate, N-vinyl caprolactam, N-methylolacrylamide, diacetone acrylamide, N-dimethyl acrylamide and N-tertiary butyl acrylamide; the monomer b is one of acrylic acid and methacrylic acid.
2. The method for constructing an intelligent catalytic membrane based on a stimulus-responsive microgel as claimed in claim 1, wherein in the step 1), the microgel material is dispersed in deionized water, and the mass concentration of the formed microgel dispersion is 0.05-0.15%; the molar concentration of the aqueous solution containing the metal catalyst ions is 0.5-2 mM; the molar ratio of the reducing agent to the metal catalyst ions is 15-40:1.
3. The method for constructing an intelligent catalytic membrane based on a stimuli-responsive microgel as claimed in claim 1, wherein in the step 2), the microporous filter membrane is one of a polypropylene membrane, a polyamide membrane, a polyethersulfone membrane, a cellulose acetate membrane, a nitrocellulose membrane, a polysulfone membrane, a polyvinylidene fluoride membrane or a polytetrafluoroethylene membrane, and the pore size distribution of the microporous filter membrane is in the range of 0.2 to 5 μm.
4. The method for constructing a smart catalytic membrane based on a stimuli-responsive microgel of claim 1, wherein the crosslinking agent is N, N-methylenebisacrylamide; the initiator is one of potassium persulfate, ammonium persulfate, azodiisobutylamidine hydrochloride, sodium persulfate, azodiiso Ding Mi hydrochloride, azodicyanovaleric acid and azodiisopropyl imidazoline hydrochloride; the surface active substance is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium oleate, potassium oleate, sodium p-styrenesulfonate, acrylamide sodium stearate, sodium allyl succinate alkyl sulfonate, dodecyl ammonium chloride and hexadecyl trimethyl ammonium bromide; the solvent is water.
5. The method for constructing a smart catalytic membrane based on a stimuli-responsive microgel of claim 1, wherein the ratio of the amounts of the substances of the monomer a, the monomer b, the crosslinking agent, the initiator and the surface active substance is 1:0.1 to 9:0.02 to 0.8:0.02 to 0.4:0.002 to 0.04; the mass ratio of the monomer a to the solvent is 1:140-420.
6. A catalysed membrane based on a stimulus responsive microgel prepared according to the method of any one of claims 1 to 5.
7. Use of a catalytic membrane according to claim 6 in a catalytic reduction process of p-nitrophenol, wherein the catalytic membrane is immobilized on a filtration device as a reaction device; adding a reducing agent sodium borohydride into the aqueous solution of the p-nitrophenol and mixing to form a reaction system, wherein the reaction system flows through a reaction device in a continuous flow mode to realize the catalytic reduction treatment of the p-nitrophenol.
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