CN111686807A - Intelligent catalytic membrane constructed based on stimuli-responsive microgel and preparation method and application thereof - Google Patents
Intelligent catalytic membrane constructed based on stimuli-responsive microgel and preparation method and application thereof Download PDFInfo
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- CN111686807A CN111686807A CN202010547898.XA CN202010547898A CN111686807A CN 111686807 A CN111686807 A CN 111686807A CN 202010547898 A CN202010547898 A CN 202010547898A CN 111686807 A CN111686807 A CN 111686807A
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- microgel
- membrane
- catalytic
- salt
- metal
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- 239000012528 membrane Substances 0.000 title claims abstract description 153
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 40
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- 239000006185 dispersion Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
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- 239000003054 catalyst Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 16
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
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- 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
- 238000001816 cooling Methods 0.000 claims description 4
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- -1 polypropylene Polymers 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
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- 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
- 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
- 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 claims description 2
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- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
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- 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
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- 238000001471 micro-filtration Methods 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
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- 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
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- 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
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- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 3
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
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- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound 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
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
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- AYKOTYRPPUMHMT-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag] AYKOTYRPPUMHMT-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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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
- 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
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- 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
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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
- 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
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- 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
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- 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
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Abstract
The application discloses an intelligent catalytic membrane constructed based on a stimuli-responsive microgel, a preparation method and an application thereof, wherein the preparation method of the intelligent catalytic membrane comprises the following steps: (1) preparing a stimulus-responsive microgel with reversible swelling/shrinking properties; (2) adding a metal salt solution into the microgel dispersion liquid, and preparing the nano metal loaded composite microgel by an in-situ reduction method; (3) dispersing the composite microgel in deionized water to form a dispersion liquid, adjusting 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 adjusting a proper stimulation condition to enable the composite microgel to swell and be firmly embedded in the microporous filter membrane, so as to prepare the intelligent catalytic membrane fixedly carrying 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 loading 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 a stimuli-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 the metal nano particles are widely applied in the field of catalysis. However, the direct use of metal nanoparticles presents a serious challenge. First, due to the large surface energy of nanoparticles, metal nanoparticles tend to agglomerate in liquids, reducing their effective surface area and increasing the average particle size, and their catalytic stability and reproducibility are often greatly affected (see ZHao M, Sun L, Crooks R M. Preparation of Cu nanocrusters with dispersion polymers Templates [ J ]. Journal of the American Chemical Society,1998, 120(19): 4877. 4878.). Secondly, the separation and recovery of the nanoparticles after the reaction is complicated and expensive. This has made it unable to meet the requirements of green chemistry and sustainable development.
The proper carrier is selected for loading the nano metal, and the method is an important means for preventing the agglomeration of the 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-aminopropyltriethoxysilane to spherical SiO2Modifying, and compounding with metal nanoparticles to obtain the composite catalyst. However, due to SiO2The microspheres are small in size (300-600 nm), are easy to agglomerate, and the use and reuse of the catalyst are still difficult. Chinese patent CN104084189A discloses an activated carbon catalyst loaded with nano metal particles and a preparation method thereof, which is easy to recover but because of the existenceThe catalytic efficiency of the nano metal in the activated carbon is reduced at higher mass transfer resistance. Chinese patent CN105536869A discloses a method for preparing a nano-silver supported hybrid microgel catalyst, the hybrid microgel is composed of PNIPAM microgel and nano-silver particles on the surface thereof, 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 problems of difficult recovery and easy loss of microgel in the using process can not be avoided.
Due to the high porosity and the micro-nano pore size distribution of the high molecular polymer membrane, fluid can effectively pass through the micro-channel of the high molecular polymer membrane, and the porous structure also provides possibility for loading nano particles, so that the catalytic membrane loaded with nano metal is expected to be constructed into a novel membrane reactor taking the high molecular polymer 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 membrane, and the catalyst is only fixed on the surface of the membrane, so that the utilization rate of the catalyst and a membrane substrate is low, and the stability of the catalyst is poor, so that the catalytic rate of the catalytic membrane prepared by the method is low, and the loss of the catalyst is easy to cause. Chinese patent CN102512991A discloses a catalytic membrane containing a metal palladium active functional layer prepared based on a layer-by-layer self-assembly technology and a preparation method thereof. The surface of the polyacrylonitrile membrane is alternately immersed in a solution containing a polyethyleneimine-palladium coordination compound and a sodium polystyrene sulfonate solution to carry out self-assembly of a membrane surface functional layer, and then in-situ reduction is carried out to generate the surface functional layer with palladium nano metal. Although the method can obtain a catalytic function layer with controllable metal amount 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) Adding a catalyst in the preparation process of the polymer membrane to obtain the catalytic membrane. The added catalyst corresponds to an additive added during membrane preparation, but often affects catalytic activity because of embedding in a membrane material or uneven distribution in the membrane. The Chinese patent CN104984668A adopts a thermal phase inversion method to prepare the nano-particle doped polyvinylidene fluoride catalytic membrane, and the nano-particle is easy to agglomerate, so that the dispersion is not uniform enough, 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 film and a preparation method thereof. And mixing the synthesized carbon-coated metal nano particles with PVDF powder, organic additives and the like, and preparing the catalytic membrane by a phase inversion method. The catalyst used as the additive of the casting solution in the method has great influence on the structure and the performance of the membrane and has narrow application range. Chinese patent CN108479412A mixes the temperature responsive microspheres carrying nano metal catalyst with polyethersulfone powder, additives, etc., and prepares the catalytic membrane by phase inversion method. The membrane pore structure can be changed along with the different addition of the hybrid polymer microspheres, and the polymer microspheres are easily embedded by the 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 the nano metal/environmental response microgel on the microporous filter membrane is rarely reported, and the catalytic performance of the catalytic membrane can be changed according to the change of the external treatment working condition, so that a better 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 loading of noble metal nano-catalyst, enhances the reaction efficiency by the principle of flow limitation, can realize effective recovery of non-renewable resources, and can provide wider application prospect in the field of catalytic membranes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an intelligent catalytic membrane constructed based on stimuli-responsive microgel and a preparation method and application thereof, the invention can effectively utilize the characteristics of high porosity and micro-nano pore size distribution of a membrane substrate, and carries nano metal/microgel into membrane pores by a dynamic filtration method to realize effective loading of a noble metal nano catalyst, and the invention also aims to realize continuous treatment on nitrophenol by constructing a flow-through reactor.
The nano metal/microgel catalytic membrane provided by the invention consists of a microporous filter membrane substrate and composite microgel which is distributed in the membrane substrate and carries a nano metal catalyst. The composite microgel loaded with the nano metal catalyst is prepared from a monomer a and a monomer b through free radical polymerization, and is composed of nano metal fixed in a microgel cross-linked network structure through in-situ reduction. In the nano metal/microgel catalytic membrane provided by the invention, the composite microgel is mainly distributed on the surface of the membrane substrate and in the pore channel; the flux and the 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 with reversible swelling/shrinking properties; (2) adding a metal salt solution into the microgel dispersion liquid, and preparing the nano metal loaded composite microgel by an in-situ reduction method; (3) dispersing the composite microgel in deionized water to form a dispersion liquid, adjusting 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 adjusting a proper stimulation condition to enable the composite microgel to swell and be firmly embedded in the microporous filter membrane, so as to prepare the intelligent catalytic membrane fixedly carrying the composite microgel.
Specifically, the technical scheme of the invention is as follows:
a method for constructing an intelligent catalytic membrane based on stimuli-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; slowly heating to 60-80 ℃ under the protection of nitrogen, reacting 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-hydroxymethyl acrylamide, diacetone acrylamide, N-dimethyl acrylamide and N-tert-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, azobisisobutylamidine hydrochloride, sodium persulfate, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline hydrochloride; the surface active substance is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium oleate, potassium oleate, sodium p-styrene sulfonate, acrylamide stearate sodium salt, sodium alkyl sulfosuccinate, dodecyl ammonium chloride and hexadecyl trimethyl ammonium bromide; the solvent is water.
The mass ratio of the monomer a to the monomer b to the cross-linking agent to the initiator to the surface active substance is 1: 0.1-9: 0.02-0.8: 0.02-0.4: 0.002-0.04, and particularly preferably 1: 0.5: 0.14: 0.1: 0.01; the mass ratio of the monomer a to the solvent is 1:140-420, and particularly preferably 1: 300.
2) Dispersing the microgel obtained in the step 1) in deionized water, adding 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, continuously reacting for 4-8 hours, and reducing metal catalyst ions loaded on the microgel into a nano metal simple substance in situ by using the reducing agent; and after the reaction is finished, centrifuging, dialyzing, freezing and drying to obtain the nano metal loaded composite microgel which is marked as a nano metal/microgel material.
The aqueous solution containing metal catalyst ions is prepared by dissolving water-soluble salt and water, wherein the water-soluble salt comprises 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 liquid is 0.05-0.15%, and particularly preferably 0.1%. The molar concentration of the aqueous solution containing the metal catalyst ion is 0.5 to 2 mM, particularly preferably 1 mM. The molar ratio of the reducing agent to the metal catalyst ion is 15-40:1, preferably 20: 1.
3) Dispersing the nano metal/microgel material obtained in the step 2) in deionization, and adjusting the pH of the formed dispersion liquid to 2-5 by hydrochloric acid; uniformly filling the nano metal/microgel material in the dispersion liquid onto a microporous filter membrane serving as a framework material by a dynamic filtration method, namely performing suction filtration on the composite microgel dispersion liquid by using the microporous filter membrane serving as the framework material; washing the surface of the membrane with deionized water after the suction filtration is finished 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 cellulose nitrate 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) Fixing the membrane obtained in the step 3) on a filtering device, filtering by using a sodium hydroxide aqueous solution with the pH =9-12, so that the nano metal/microgel material is swelled and firmly embedded in the microporous filter membrane, and 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.
The flux and the catalytic performance of the intelligent catalytic membrane immobilized with the nano metal/microgel material change along with the change of the response environmental conditions. Therefore, when the intelligent catalytic membrane provided by the invention is used for treating nitrophenol, the sodium borohydride is used as a reducing agent, a reaction system is an alkali environment, and the nano metal/microgel material in the catalytic membrane swells, so that the catalytic performance of the catalytic membrane can be improved, and efficient catalysis can be realized. Specifically, the reaction solution system flows through a reaction device (a catalytic membrane is fixed on a filtering device and used as the reaction device) in a continuous flow mode through a peristaltic pump, effluent liquid is collected, and the conversion rate of p-nitrophenol is calculated by adopting a liquid chromatography so as to evaluate the catalytic performance.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is to load the environmental response microgel loaded with the nano metal catalyst into the membrane substrate sold in the market. In the preparation process of the environmental response type 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 the stability of the catalytic membrane are improved. And 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 loading 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, because a large amount of environment-responsive microgel loaded with the nano metal catalyst is distributed in the membrane substrate, the particle size of the environment-responsive microgel loaded with the nano metal catalyst can change along with the change of environmental conditions, and the flux and the catalytic performance of the catalytic membrane also change along with the change of the environmental conditions. When the intelligent catalytic membrane carries out continuous catalytic treatment on a reaction liquid system, the composite microgel can swell and increase the particle size through reasonably adjusting the environmental conditions (namely reasonably adjusting the pH value of the reaction liquid system), so that more nano metal catalysts loaded on the microgel are exposed on the surface of the 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, and has the advantages of easy satisfaction of conditions such as reaction process environment temperature and the like, simple and convenient method, high efficiency, lower cost and easy realization of industrialization.
4. The intelligent catalytic membrane prepared by the invention can be constructed into a flow-through reactor, realizes continuous treatment of reactants, avoids the traditional filtering and centrifuging means adopted by the catalyst in post-treatment, and realizes green reaction of catalysis and separation at one time. The catalytic membrane and the preparation method thereof not only solve the problems that the noble metal nano catalyst is difficult to disperse and easy to lose, but also can effectively improve the catalytic efficiency, and have great potential in industrial production and application.
Drawings
FIG. 1a is a transmission electron micrograph of a microgel of example 1;
FIG. 1b is a TEM image of the Ag nanoparticle-loaded composite microgel of example 1;
FIG. 2a is a scanning electron micrograph of a cross section of a blank polysulfone microfiltration membrane according to example 1;
FIG. 2b is a scanning electron microscope cross-sectional view of the polysulfone microporous filtration membrane loaded with the composite microgel of example 1;
FIG. 3 is an EDS chart of the polysulfone microporous filter membrane having the composite microgel immobilized therein of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
The preparation of the smart catalytic membrane in this example was carried out 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; and under the protection of nitrogen, putting the mixture into a constant-temperature oil bath kettle at 70 ℃ for heating reaction for 4 hours, cooling the mixture to room temperature, centrifuging the mixture, and freeze-drying the mixture to obtain the microgel.
(2) Weighing 100 mg of the microgel obtained in the step (1), dispersing in 200 mL of 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 dripped dropwise, and the reaction is continued for 4 hours; after the reaction is finished, centrifuging, dialyzing, freezing and drying to obtain the composite microgel loaded with the nano Ag;
(3) weighing the composite microgel obtained in the step (2) and dispersing the composite microgel in deionized water, wherein the mass concentration of the microgel dispersion liquid is 0.001%, and regulating the pH of the dispersion liquid to 3 by using hydrochloric acid; 500mL of composite microgel dispersion is evenly pumped and filtered to polysulfone particlesThe effective filtration area on the porous filter membrane is 12.56 cm2(ii) a Washing the surface of the membrane with deionized water after the suction filtration is finished to obtain a treated membrane;
(4) and (4) fixing the membrane obtained in the step (3) on a filtering device, and filtering the membrane by using a NaOH aqueous solution with the pH =9-12 to enable the composite microgel to swell and be firmly embedded in the microporous filter membrane, so that the intelligent catalytic membrane is prepared.
FIG. 1a is a TEM image of a microgel prepared in step (1) of example 1, and FIG. 1b is a TEM image of a Ag nanoparticle-loaded composite microgel prepared in step (2). Comparing fig. 1a and fig. 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 Ag nanoparticle-loaded composite microgel.
FIG. 2a is a scanning electron microscope cross-sectional view of a blank polysulfone microporous filtration membrane commercially available in example 1, and FIG. 2b is a scanning electron microscope cross-sectional view of a polysulfone microporous filtration membrane immobilized with a composite microgel prepared in step (3) of example 1. By comparing fig. 2a and fig. 2b, it is evident that a large amount of the composite microgel is distributed in the inner pores of the microporous filter membrane, which also proves the success of the method for immobilizing the composite microgel on the commercial microporous filter membrane.
FIG. 3 is an EDS chart of the microporous filtration membrane immobilized with the composite microgel prepared in step (3) of example 1, and the results of the tests show that Ag element is actually present on the membrane.
Example 2
The preparation steps of the intelligent catalytic membrane of example 2 are 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; and under the protection of nitrogen, putting the mixture into a constant-temperature oil bath kettle at 70 ℃ for heating reaction for 4 hours, cooling the mixture to room temperature, centrifuging the mixture, and freeze-drying the mixture to obtain the microgel.
(2) Weighing the microgel obtained in the step (1) and dispersing the microgel in deionized waterThe mass concentration of the colloidal dispersion is 0.001%, and the pH of the dispersion is adjusted to 3 by hydrochloric acid; 500mL of microgel dispersion is evenly filtered on a polysulfone microporous filter membrane in a suction way, and the effective filtration area is 12.56 cm2(ii) a Washing the surface of the membrane with deionized water after the suction filtration is finished to obtain a treated membrane;
(3) and (3) fixing the membrane obtained in the step (2) on a filtering device, and filtering the membrane by using a NaOH aqueous solution with the pH =9-12 to swell the microgel and firmly inlay the microgel in the microporous filter membrane, thereby obtaining the intelligent catalytic membrane.
It can be seen that the preparation steps of the smart catalytic membrane of example 2 are different from those of example 1 only in that "the preparation process of example 2 without loading nano Ag" is performed, and other steps and parameters are the same as those of example 1.
Example 3
Preparation procedure of smart catalytic membrane of example 3 example 1 was repeated except for "replacing the volume of the composite microgel dispersion filtered in step (3) of example 1 with 100mL from 500 mL", and the other procedures and parameters were the same as in example 1.
Example 4
Procedure for preparation of smart catalyst membrane of example 4 example 1 was repeated except for "replacing 1 mM silver nitrate aqueous solution with platinum chloride aqueous solution of the same molarity in step (2) of example 1", and other procedures and parameters were the same as in example 1.
Example 5
Procedure for preparation of smart catalyst membrane of example 5 example 1 was repeated except for "replacing 1 mM silver nitrate aqueous solution with palladium chloride aqueous solution of the same molar concentration in step (2) of example 1", and other procedures and parameters were the same as in example 1.
Example 6
Procedure for preparation of smart catalyst membrane of example 6 example 1 was repeated except for "replacing 1 mM silver nitrate aqueous solution with gold chloride aqueous solution of the same molarity in step (2) of example 1", and other procedures and parameters were the same as those of example 1.
Example 7
Procedure for preparation of smart catalyst membrane of example 7 example 1 was repeated except for "replacing 1 mM silver nitrate aqueous solution with nickel chloride aqueous solution of the same molarity in step (2) of example 1", and other procedures and parameters were the same as in example 1.
Example 8
Procedure for preparation of smart catalyst membrane of example 8 example 1 was repeated except for "replacing 1 mM silver nitrate aqueous solution with cobalt chloride aqueous solution of the same molar concentration in step (2) of example 1", and other procedures and parameters were the same as those of example 1.
Example 9
Procedure for preparation of smart catalyst membrane of example 9 example 1 was repeated except for "replacing 1 mM silver nitrate aqueous solution with copper chloride aqueous solution of the same molarity in step (2) of example 1", and other procedures and parameters were the same as in example 1.
Example 10
Procedure for preparation of smart catalyst membrane of example 10 example 1 was repeated except for "replacing 1 mM silver nitrate aqueous solution with ruthenium chloride aqueous solution of the same molarity in step (2) of example 1", and other procedures and parameters were the same as in example 1.
Application example 11
And (3) testing the catalytic performance of the catalytic membrane:
in the application example, sodium borohydride is used for reducing p-nitrophenol to serve as a model reaction to illustrate the application effect of the prepared catalytic membrane in catalytic treatment, and the conversion rate of the p-nitrophenol is mainly considered.
The transmembrane catalysis test was carried out by using a flow-through reaction apparatus (i.e., a filtration apparatus), and the catalytic membranes prepared in examples 1 to 10 were cut into suitable sizes and fixed on the filtration apparatus, and the reaction solution (p-nitrophenol substance concentration of 1.4 × 10) was stored in a liquid storage tank-4M and sodium borohydride substances with the quantitative concentration of 0.15M and water as a solvent) flow through the reaction device in a continuous flow mode through a peristaltic pump, and the retention time of the reaction liquid on the catalytic membrane is controlled to be 2 seconds by adjusting the rotating speed of the peristaltic pump. Experiment to be stabilizedAfter 2 hours, effluent liquid is collected, the conversion rate of p-nitrophenol is calculated by liquid chromatography, and the catalytic performance is evaluated according to the conversion rate of p-nitrophenol. The results of the conversion rates of p-nitrophenol when the catalytic membranes prepared in examples 1 to 10 were applied to the catalytic reaction of p-nitrophenol are shown in table 1.
As can be seen from table 1, comparative example 1 and example 2, the catalytic membrane exhibited excellent catalytic performance when it was immobilized with the composite microgel containing Ag nanoparticles, while the catalytic membrane was completely free of catalytic activity when it was not immobilized with the microgel of Ag nanoparticles, which further confirmed that the Ag nanocatalyst was stably supported on the membrane.
As can be seen from table 1, comparing example 1 and example 3, the catalytic performance of the catalytic membrane increases as the loading amount of the composite microgel increases, because more composite microgel provides more catalytically active sites, which is advantageous for increasing the reaction rate. Comparative examples 4-10 show that the method of the present invention is applicable to many nanometals, and that different nanometals have different catalytic activities, which also indicates the universality of the method.
Example 1 flow-through reactor with catalyst membrane Assembly, reaction solution (p-nitrophenol concentration: 1.4 × 10)-4M and sodium borohydride with the mass concentration of 0.15M and water as solvent) continuously flow through a flow-through reaction device to carry out continuous catalytic reduction treatment on nitrophenol. The effluent from the 10h experiment was collected and the conversion of p-nitrophenol was calculated by liquid chromatography and the results are shown in table 2.
From table 2, comparing the continuous use catalytic effect of the catalytic membrane, when the catalytic membrane still maintains good catalytic performance after continuous use for 10 hours, it is confirmed that the catalytic membrane has excellent stability, the nano catalyst is effectively immobilized in the membrane, and the catalytic performance is stable, which can satisfy the continuous use condition.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (9)
1. A method for constructing an intelligent catalytic membrane based on a stimuli-responsive microgel is characterized by comprising the following steps:
1) dispersing the microgel with reversible swelling-shrinking property in deionized water, adding aqueous solution containing metal catalyst ions, and mechanically stirring at room temperature for 1-6 hours; then, under the protection of nitrogen, slowly dropwise adding a reducing agent solution, continuously reacting for 4-8 hours, and reducing metal catalyst ions loaded on the microgel into a nano metal simple substance in situ by using the reducing agent; after the reaction is finished, performing centrifugation, dialysis and freeze drying to obtain the nano metal loaded composite microgel which is marked as a 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 value 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 fill the nano metal/microgel material on the microporous filter membrane serving as a framework material; washing the membrane surface of the microporous filter membrane by using deionized water after the filtration is finished to obtain a treated microporous filter membrane;
3) fixing the microporous filter membrane treated in the step 3) on a filtering device, filtering by alkali liquor with pH =9-12, so that the nano metal/microgel material is swelled and firmly embedded in the microporous filter membrane serving as a framework material, and thus obtaining the intelligent catalytic membrane product immobilized with the nano metal/microgel material.
2. The method for constructing a smart catalyst membrane based on a stimuli-responsive microgel of claim 1, wherein in step 1), the aqueous solution containing metal catalyst ions is prepared by dissolving a 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.
3. The method as claimed in claim 1, wherein the microgel material is dispersed in deionized water in the step 1) to form a microgel dispersion with a mass concentration of 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 ion is 15-40: 1.
4. The method as set forth in claim 1, wherein in the step 2), the microfiltration membrane is one of polypropylene, polyamide, polyethersulfone, cellulose acetate, nitrocellulose, polysulfone, polyvinylidene fluoride, or polytetrafluoroethylene, and has a pore size distribution ranging from 0.2 μm to 5 μm.
5. The method for constructing a smart catalytic membrane based on a stimuli-responsive microgel as claimed in claim 1, wherein in step 1), the microgel with reversible swelling-shrinking property is prepared by: 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.
6. The method for constructing a smart catalyst membrane based on a stimuli-responsive microgel according to claim 5, wherein the monomer a is at least one of acrylamide, N-isopropylacrylamide, N-dimethylaminoethylmethacrylate, N-vinylcaprolactam, N-methylolacrylamide, diacetone acrylamide, N-dimethylacrylamide and N-t-butylacrylamide; 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, azobisisobutylamidine hydrochloride, sodium persulfate, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline hydrochloride; the surface active substance is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium oleate, potassium oleate, sodium p-styrene sulfonate, acrylamide stearate sodium salt, sodium alkyl sulfosuccinate, dodecyl ammonium chloride and hexadecyl trimethyl ammonium bromide; the solvent is water.
7. The method of claim 5, wherein the amount ratio of the monomer a, the monomer b, the crosslinking agent, the initiator, and the surfactant is 1: 0.1-9: 0.02-0.8: 0.02-0.4: 0.002-0.04; the mass ratio of the monomer a to the solvent is 1: 140-420.
8. A stimuli-responsive microgel based catalytic membrane prepared according to the method of any one of claims 1 to 7.
9. Use of a catalytic membrane according to claim 8 in the catalytic reduction of p-nitrophenol, wherein the catalytic membrane is fixed to a filter unit as a reaction unit; adding reducing agent sodium borohydride into the water 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 catalytic reduction treatment of the p-nitrophenol.
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