CN108940374A - The preparation method and application of fiber composite film catalyst - Google Patents
The preparation method and application of fiber composite film catalyst Download PDFInfo
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- CN108940374A CN108940374A CN201810593194.9A CN201810593194A CN108940374A CN 108940374 A CN108940374 A CN 108940374A CN 201810593194 A CN201810593194 A CN 201810593194A CN 108940374 A CN108940374 A CN 108940374A
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- 239000000835 fiber Substances 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 76
- 239000000243 solution Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 33
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 33
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 33
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 33
- 235000019441 ethanol Nutrition 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- 229920002678 cellulose Polymers 0.000 claims description 23
- 239000001913 cellulose Substances 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 16
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000006266 etherification reaction Methods 0.000 claims description 13
- 238000005956 quaternization reaction Methods 0.000 claims description 13
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000013110 organic ligand Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 6
- 241001330002 Bambuseae Species 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 6
- 229920000875 Dissolving pulp Polymers 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000011121 hardwood Substances 0.000 claims description 6
- 238000005360 mashing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229940096017 silver fluoride Drugs 0.000 claims description 6
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- -1 silver ions Chemical class 0.000 claims description 5
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 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 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 229920003043 Cellulose fiber Polymers 0.000 abstract description 13
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical group NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 230000011987 methylation Effects 0.000 abstract description 4
- 238000007069 methylation reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000002082 metal nanoparticle Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013084 copper-based metal-organic framework Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229960005489 paracetamol Drugs 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008953 bacterial degradation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 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 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The preparation method of fiber composite film catalyst, preparation step is as follows: cellulose fibre being carried out carboxy methylation processing first, introduce a large amount of carboxylic group, it is stirred metal organic frame MOFs fabricated in situ on fiber secondly by dipping, then nanometer Ag (Ag NPs) load is dispersed on MOFs by microwave reduction, it finally by washing, filters, forming of manufacturing paper with pulp obtains nanometer paper group compound film catalysis material；Wherein the partial size of Ag nanoparticle is between 6~20nm, and can be realized by the synergistic effect with MOFs by p-nitrophenol quick catalysis Degradation and Transformation in waste water is para-aminophenol, and a high conversion rate is up to 99% or more；It compared to traditional beaded catalyst, solves the problems, such as that its recycling is difficult, and catalysis time is short, high-efficient, can be used as filler and mix to manufacture paper with pulp with other plant fiber and prepare catalytic membrane material, be with a wide range of applications handling industrial wastewater field.
Description
Technical field
The invention belongs to nanocomposite preparation and catalytic degradation technology field more particularly to fiber composite film catalysts
Preparation method and application.
Background technique
With the continuous development of industry, in global range, serious water pollution is continuously emerged in especially developing country
Problem.Water pollution problems, which becomes in environmental improvement work, to be first had to solve the problems, such as.Phenol wastewater is since it is with high toxicity, difficulty
It is longer with degradation, complicated component and in the environment residence time, it is the main source for causing water pollution.With p-nitrophenol
For, as main medical material for producing medicine intermediate p-nitrophenyl phenolic ether and one-step synthesis anti-inflammatory analgesic object pair
Paracetamol, and produce the raw material of pesticide and the by-product of production nitrobenzene.Therefore, the waste water containing p-nitrophenol is main
From medicine, chemical industry, petroleum and agricultural.This kind of waste water has the following characteristics that strong toxicity, carcinogenic, teratogenesis, mutagenesis and is difficult to
Biodegrade etc., serious polluted-water environment bring serious harm to people's lives and health.So having to pass through conjunction
Reason, effective processing further could reuse or be discharged into water body.The method for being used to be catalyzed p-nitrophenol at present is main
There are chemical oxidization method, chemical precipitation method, bacterial degradation processing and absorption method processing, but these method typically costs are higher and locate
It is poor to manage effect.Compared to the above method, p-nitrophenyl is restored using metal nanoparticle (such as Ag, Au, Pd) catalyst
It is a kind of that the rapid catalytic conversion of p-nitrophenol, a high conversion rate, and reduzate para-aminophenol, which may be implemented, in phenol
Important industrial chemicals and organic intermediate can be widely applied for medical (such as paracetamol), antioxidant, dyestuff, sense
Synthesis of fine chemicals such as luminescent material and pesticide etc. has very high application value.But metal nanoparticle by
It is larger in specific surface area, so being easy to happen reunion, greatly reduce its catalytic performance.On the other hand, many metal nanos are urged
Agent is due to being all granular solids, so recovery difficult is big, influences its reuse.
The Chinese patent literature of Publication No. [CN106916110A] discloses a kind of using metal-organic framework material
(ZIF-67) method of monodisperse metal nanoparticles (Pb, Pt, Au) is loaded.The aqueous solution of inorganic noble metal acid is added first
It is impregnated into the suspension of metal organic frame, reducing agent stirring is then added.Metal nanoparticle is fine in product
Be dispersed in the duct of MOFs material, particle size is 3~4nm or so.This method step is simple, shows MOFs material pair
Metal nanoparticle has dispersibility well.But as granular pattern catalyst, it is also faced in terms of recycling very big
Challenge.
The Chinese patent literature of Publication No. [CN106345462A] discloses a kind of meso-porous nano carbon load dispersion gold
Nanoparticle is used to be catalyzed the preparation method of p-nitrophenol, by mixing soluble carbon source with surfactant, then
The mixture of organosilicon and gold salt is added, carries out hydro-thermal reaction after mixing evenly, obtains catalysis material after filtering, drying, calcining.
Gold nano grain is stably dispersed in mesoporous carbon spheres skeleton, and particle size is uniform, is shown in catalysis p-nitrophenol experiment
Good catalytic performance.But complicated operation for this method, likewise, being difficult to realize efficiently return as granular pattern catalyst
It receives.
The present invention is acted on by Coordinative Chemistry key MOFs being anchored on already carboxymethylated fibres using cellulose fibre as template
On, Ag ion is then reduced to by nano Ag particles by Microwave reduction method in situ, and then load and be dispersed on MOF.On the one hand
The reunion of nano Ag particles is avoided, on the other hand the urging rapidly and efficiently by the collaboration transfer electronic action of nanometer Ag and MOFs
Change conversion nitrophenol.For the nano combined film catalyst compared to conventional particles catalyst, recycling is easy, is also used as function
Filler and other unmodified cellulose fiber blends, which are manufactured paper with pulp, prepares paper base filter membrane catalysis material, has in processing industrial wastewater field
Have wide practical use.
Summary of the invention
To overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of preparations of fiber composite film catalyst
Method and application, 1) the carboxy methylation processing of cellulose fibre；2) infusion process fabricated in situ Metal-organic frame (Cu-MOFs)
In on modified fibre；3) nanometer Ag load is dispersed on MOFs by microwave reduction, is solved catalyst with metal nanoparticles and is easily rolled into a ball
Poly- the problem of causing catalytic performance to reduce, recycling is simple, high catalytic efficiency
To achieve the above object, the technical solution adopted by the present invention is that: the preparation method of fiber composite film catalyst, including following
Step:
1) sodium hydroxide solution 5 that by mass percentage, addition concentration is 15~25% in 0.5~2g cellulose paste~
10mL carries out quaternization at normal temperature, and after reacting 2~4h, adding 5~10mL concentration is 20~25% sodium chloroacetate solutions
Etherification reaction is carried out at a temperature of 40~60 DEG C, reacts 3~5h, is finally washed fiber with dehydrated alcohol at room temperature and is obtained to neutral
To carboxymethyl cellulose；
2) N,N-dimethylformamide (DMF) of two parts of 100mL is configured, the mixed solution of second alcohol and water is denoted as solution A and B is molten
Liquid, n,N-Dimethylformamide DMF, second alcohol and water volume ratio be 1:1:1；Cu system metal salt, Cu ion are added in solution A
Concentration is 0.0043mM, and organic ligand is added in B solution, and Cu ion and organic ligand molar ratio are 1:3, are sufficiently stirred；Claim
1~3g carboxymethyl cellulose is taken first to impregnate 30~120 min in solution A, then 30~120 min in being transferred to B solution, weight
Complex Alternating impregnates 4~6 times；Carboxymethyl cellulose impregnates to 4 hours after the completion of dipping in 100mL methylene chloride, finally 60~
At 80 DEG C be dried in vacuo 3~5h, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose, be denoted as MOFs/ fibre
Dimension；
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and weighing concentration of silver ions is 60~80mM
Ag system metal salt be added mixed solution in, be sufficiently stirred；MOFs/ fiber prepared by step 2 is added to above-mentioned mixed solution
In be sufficiently impregnated 6~8h of stirring, then filter out fiber, nanometer Ag restored into load using Microwave reduction method and is dispersed in
On MOFs；Finally sample is washed with deionized 5~8 times, is filtered, forming of manufacturing paper with pulp obtains paper base filter membrane material.
The cellulose paste uses cotton dissolving pulp, DQP bleached bamboo pulp or hardwood pulp, and cellulose paste passes through slurry
The cellulose paste that mass fraction is 2~10% is made in dispersion.
The mass ratio of quaternization sodium hydroxide and fibre stuff is 0.5~1.25:1g, in etherification reaction sodium chloroacetate with
The mass ratio of fibre stuff is 1~2:1g；
The n,N-Dimethylformamide (DMF), the volume ratio of second alcohol and water are 1:1:1, and Cu system metal salt uses nitre
Sour copper, copper acetate, copper sulphate or copper chloride；Organic ligand is trimesic acid or terephthalic acid (TPA)；The fiber impregnation time is 30
~120min.
The Ag system metal salt use silver nitrate, sulfate or silver fluoride, be added solution after concentration of silver ions be 60~
80mM, 5~8h of dipping stirring.
Microwave reduction method used, the power of microwave reduction are 600~800w, and the recovery time is 10~20 minutes.
Another object of the present invention is the p-nitrophenol being used for above-mentioned catalyst in catalytic degradation waste water.
The present invention has technical effect beneficial below compared with existing metal nano catalyst:
The present invention relates to preparation nanometer Ag/metal organic frame/cellulose fibre film catalyst methods and application；This hair
It is bright Cu-MOF can be supported on fiber by chemical bond after fiber carboxy methylation using cellulose fibre as template,
Then the load of nanometer Ag in-situ reducing is dispersed on MOF by Microwave reduction method, the partial size of Ag nanoparticle 6~20nm it
Between, the reunion of nanoparticle is on the one hand avoided, it is quickly high on the other hand to shift electronic action by the collaboration of nanometer Ag and MOF
The catalyzed conversion p-nitrophenol of effect, for a high conversion rate up to 99% or more, transformation frequency (TOF) value is up to 559.2h-1.Tradition
Metal nano catalyst is largely graininess, so recycling is relatively difficult, the present invention is recycled as a kind of fiber film catalyst
The catalytic efficiency of simplicity, recycling is higher, keeps 92% or more catalytic efficiency for circulation 5 times, still in addition it can as filling out
Material manufactures paper with pulp with other plant fiber blend and prepares catalytic membrane, is with a wide range of applications in processing industrial wastewater field.
Detailed description of the invention
Fig. 1 is that Metal-organic frame (MOFs) prepared by the embodiment of the present invention 1 is supported on the scanning on cellulose fibre
Electron microscope (SEM).
Fig. 2 is that nanometer Ag prepared by the embodiment of the present invention 1 is dispersed in the transmission electron microscope picture (TEM) on MOFs.
Fig. 3 is size distribution plot of the Ag nanoparticle of the preparation of the embodiment of the present invention 1 on MOFs.
Fig. 4 is the X-ray diffraction of Ag NPs/MOFs/ cellulose fibre film catalyst prepared by the embodiment of the present invention 1
Scheme (XRD).
Fig. 5 is the UV, visible light of Ag NPs/MOFs/ cellulose fibre film catalyst prepared by the embodiment of the present invention 1
Abosrption spectrogram (UV-vis).
Fig. 6 is the pictorial diagram of Ag NPs/MOFs/ cellulose fibre composite membrane prepared by the embodiment of the present invention 1.
Fig. 7 be the embodiment of the present invention 1 prepare Ag NPs/MOFs/ cellulose fibre film catalyst can reuse figure.
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below.These examples are merely to illustrate this
It invents rather than limits the scope of the invention, after the present invention has been read, those skilled in the art are to of the invention various
The modification of equivalent form is fallen within the scope of the restriction of the application appended claims.
Embodiment 1
The preparation method of fiber composite film catalyst, comprising the following steps:
1) cotton dissolving pulp is chosen, is dispersed by mashing, the cellulose paste that mass fraction is 4% is made；In 1g cellulose paste
Addition 5ml concentration is 15% sodium hydroxide solution, carries out quaternization at normal temperature, and after reacting 3h, adding 5ml concentration is 20%
Sodium chloroacetate solution carry out etherification reaction at 60 DEG C, react 4h, finally wash fiber into dehydrated alcohol at room temperature
Property obtains carboxymethyl cellulose；
2) N,N-dimethylformamide (DMF) of two parts of 100ml is configured, the mixed solution of second alcohol and water is denoted as solution A and B is molten
Liquid, n,N-Dimethylformamide (DMF), the volume ratio of second alcohol and water are 1:1:1；2g copper acetate is added in solution A, it is molten in B
1g trimesic acid is added in liquid, is sufficiently stirred；The carboxymethyl cellulose for weighing 2g first impregnates 30min in solution A, is then turning
It moves on to and impregnates 30min in B solution, repeat alternating impregnating 5 times；After the completion of dipping by carboxymethyl cellulose in 100ml methylene chloride
Impregnate 4 hours, be finally dried in vacuo 4h at 70 DEG C, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose,
It is denoted as MOFs/ fiber.
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and the silver nitrate for weighing 0.5g is added
In mixed solution, it is sufficiently stirred；MOFs/ fiber prepared by step 2 is add to the above mixed solution and is sufficiently impregnated stirring
Then 6h filters out fiber, fiber is placed under the microwave of 700w and restores 15min, and nanometer Ag can restore load dispersion
On MOF；It is finally washed with deionized 6 times, filters, forming of manufacturing paper with pulp obtains paper-based membrane catalysis material.
Sample topography is characterized using SEM, TEM, XRD, it can be seen that MOF material from Fig. 1 scanning electron microscope image
In complete shape of octahedron, it is evenly distributed in the surface of carboxymethyl cellulose, load capacity reaches 31.64%.Electricity is transmitted from Fig. 2
It can be seen that Ag nanoparticle is uniformly immobilized in the surface and duct of MOFs in mirror image, good dispersibility is showed.From
The grain size distribution of Fig. 3 can be seen that the particle size of nanometer Ag is smaller, largely be distributed between 6~20nm.The XRD of Fig. 4
Figure can be seen that 2 θ=6.7 ° of nanometer Ag/MOF characteristic peak in (b), and 9.5 °, 11.7 °, 13.3 °, 18.9 °, 25.8 ° go out
Now in (d), show that nanometer Ag/metal organic frame@cellulosic fibre material is successfully prepared out.
Embodiment 2
The preparation method of fiber composite film catalyst, comprising the following steps:
1) DQP bleached bamboo pulp is chosen, is dispersed by mashing, the cellulose paste that mass fraction is 6% is made；In 0.5g slurry
Addition 8ml concentration is 20% sodium hydroxide solution, carries out quaternization at normal temperature, and after reacting 2h, adding 8ml concentration is
25% sodium chloroacetate solution carries out etherification reaction at 50 DEG C, reacts 3h, finally washs fiber extremely with dehydrated alcohol at room temperature
Neutrality obtains carboxymethyl cellulose；
2) DMF of two parts of 100ml is configured, the mixed solution of second alcohol and water is denoted as solution A and B solution, n,N-Dimethylformamide
(DMF), the volume ratio of second alcohol and water is 1:1:1；2g copper nitrate is added in solution A, 1g terephthaldehyde is added in B solution
Acid is sufficiently stirred；The carboxymethyl cellulose for weighing 1g first impregnates 60min in A liquid, then impregnates 60min in being transferred to B liquid,
It repeats alternating impregnating 6 times；Carboxymethyl cellulose is impregnated 4 hours in 100ml methylene chloride after the completion of dipping, finally at 80 DEG C
Be dried in vacuo 5h, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose, be denoted as MOFs/ fiber.
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and the silver sulfate for weighing 1g, which is added, to be mixed
It closes in solution, is sufficiently stirred；MOFs/ fiber prepared by step 2 is add to the above mixed solution and is sufficiently impregnated stirring 8h,
Then fiber is filtered out, fiber is placed in reductase 12 0min under the microwave of 800w, nanometer Ag can restore load and be dispersed in
On MOFs；It is finally washed with deionized 5 times, filters, forming of manufacturing paper with pulp obtains paper-based membrane catalysis material.
Embodiment 3
The preparation method of fiber composite film catalyst, comprising the following steps:
1) hardwood pulp is chosen, is dispersed by mashing, the cellulose paste that mass fraction is 10% is made；In 2g cellulose paste
The middle sodium hydroxide solution that 10ml concentration is added and is 25%, carries out quaternization at normal temperature, after reacting 4h, it is dense to add 10ml
Degree carries out etherification reaction for 25% sodium chloroacetate solution at 40 DEG C, reacts 5h, finally washs fibre with dehydrated alcohol at room temperature
Dimension to neutrality obtains carboxymethyl cellulose；
2) n,N-Dimethylformamide (DMF) of two parts of 100ml is configured, the mixed solution of second alcohol and water is denoted as solution A and B is molten
Liquid, n,N-Dimethylformamide (DMF), the volume ratio of second alcohol and water are 1:1:1；2g copper sulphate is added in solution A, it is molten in B
1g terephthalic acid (TPA) is added in liquid, is sufficiently stirred；The carboxymethyl cellulose for weighing 3g first impregnates 120min in A liquid, is then turning
It moves on in B liquid and impregnates 120min, repeat alternating impregnating 4 times；Fiber is impregnated to 4 in 100ml methylene chloride small after the completion of dipping
When, be finally dried in vacuo 3h at 60 DEG C, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose, be denoted as
MOFs/ fiber；
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and mixing is added in the silver fluoride for weighing 0.6g
In solution, it is sufficiently stirred；The MOFs/ fiber of step 2 step preparation is added in above-mentioned solution and is sufficiently impregnated stirring 8h, then
Fiber is filtered out, fiber is placed under the microwave of 600w and restores 10min, nanometer Ag can restore load and be dispersed in MOFs
On；Last deionized water is washed 8 times, is filtered, and forming of manufacturing paper with pulp obtains paper-based membrane catalysis material.
In order to prove beneficial effects of the present invention, the catalyst prepared in embodiment 1 is now used for catalytic degradation to nitro
Phenol, steps are as follows:
Film catalyst prepared by embodiment 1 is thrown into the p-nitrophenyl that 300ml concentration is 0.1mM according to the ratio of 5mg/L
In phenol solution, 113mg sodium borohydride is added, reaction carries out at room temperature, and about 10min or so, p-nitrophenol can be complete
Portion is converted into para-aminophenol.Absorbing spectrogram from the UV of Fig. 5 can be seen that the progress with reaction, the absorption peak at 400nm
(p-nitrophenol) gradually decreases, and the absorption peak at 300nm gradually rises (para-aminophenol), fully reacting after 10min.Figure
6 be catalyzed p-nitrophenol actual device figure, Fig. 7 be film catalyst can reuse figure.
The cellulose paste uses cotton dissolving pulp, DQP bleached bamboo pulp or hardwood pulp, and cellulose paste passes through slurry
The cellulose paste that mass fraction is 2~10% is made in dispersion.
The mass ratio of quaternization sodium hydroxide and fibre stuff is 0.5~1.25:1g, in etherification reaction sodium chloroacetate with
The mass ratio of fibre stuff is 1~2:1g；
The n,N-Dimethylformamide (DMF), the volume ratio of second alcohol and water are 1:1:1, and Cu system metal salt uses nitre
Sour copper, copper acetate, copper sulphate or copper chloride；Organic ligand is trimesic acid or terephthalic acid (TPA)；The fiber impregnation time is 30
~120min.
The Ag system metal salt use silver nitrate, sulfate or silver fluoride, be added solution after concentration of silver ions be 60~
80mM, 5~8h of dipping stirring.
Microwave reduction method used, the power of microwave reduction are 600~800w, and the recovery time is 10~20 minutes.
The carboxy methylation of cellulose fibre is handled:
15~25% sodium hydroxide solutions are added in 0.5~2g cellulose paste, carry out quaternization at normal temperature, reaction 2~
After 4h, adds sodium chloroacetate solution and carry out etherification reaction at a temperature of 40~60 DEG C, react 3~5h, finally use at room temperature
Dehydrated alcohol washing fiber to neutrality obtains carboxymethyl cellulose.
The cellulose paste of selection includes that cotton dissolving pulp, DQP bleached bamboo pulp, hardwood pulp are made and starch by discongesting dispersion
Expect that concentration is 2~10% slurry.
The mass ratio of quaternization sodium hydroxide and fibre stuff is 0.5~1.25:1g, and sodium hydroxide quality is preferably
1g。
The mass ratio of sodium chloroacetate and fibre stuff is 1~2:1g in etherification reaction.Sodium chloroacetate quality is preferably 1.5g.
1) infusion process fabricated in situ Cu-MOFs is on modified fibre
The DMF of two parts of 100ml is configured, the mixed solution of second alcohol and water is denoted as A and B.Cu system metal salt is added in solution A, in B
Organic ligand is added in solution, is sufficiently stirred.1~3g carboxymethyl cellulose first time of infusion in A liquid is weighed, is then being turned
It moves on in B liquid and impregnates, repeat alternating impregnating 4~6 times.Fiber is impregnated 4 hours in 100ml methylene chloride after the completion of dipping,
3~5h is finally dried in vacuo at 60~80 DEG C.
DMF, the volume ratio of second alcohol and water are 1:1:1, Cu system metal salt can for copper nitrate, copper acetate, copper sulphate,
Copper chloride etc..Wherein the mass ratio of Cu system metal salt and organic ligand is 1.5~2.5:1, and Cu system metal salt quality is preferably 2g.
Organic ligand can be trimesic acid, terephthalic acid (TPA) etc..The fiber impregnation time is 30~60min.
2) nanometer Ag load is dispersed on MOFs by microwave reduction
The mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, weigh the addition of a certain amount of Ag system metal salt
In mixed solution, concentration 60mM is sufficiently stirred.Fiber (0.5~2g) after drying is added in above-mentioned solution and is sufficiently soaked
Stain stirring, then filters out fiber, nanometer Ag is restored load using Microwave reduction method and is dispersed on MOFs.Finally by sample
Product are washed with deionized 5~8 times, filter, and molding of manufacturing paper with pulp obtains membrane material.
Ag system metal salt can be silver nitrate, sulfate, silver fluoride etc., 5~8h of dipping stirring.Preferably 6h.
Microwave reduction power used is 600~800w, and the recovery time is 10~20 minutes.
Nanometer Ag/metal organic frame/cellulose fibre film catalyst is used for catalytic degradation p-nitrophenol, specifically
Steps are as follows:
By film catalyst according to the ratio of 2mg/L~5mg/L throw into concentration be 0.1mM~0.25mM p-nitrophenol it is molten
In liquid, sodium borohydride is added according to certain molar ratio, reaction carries out at room temperature.Reaction time is 6min~10min or so
P-nitrophenol can all be reduced to para-aminophenol.
Wherein the molar ratio of p-nitrophenol and sodium borohydride is 1:50~100.
In p-nitrophenol Catalysis experiments, nanometer Ag and MOF play the role of collaboration transfer electronics, in reducing agent boron
In the presence of sodium hydride, BH4 -Electronics is transferred to p-nitrophenol by nanometer Ag and MOF, so as to complete p-nitrophenol
It is restored to the quick catalysis of para-aminophenol.
Claims (10)
1. the preparation method of fiber composite film catalyst, which comprises the following steps:
1) sodium hydroxide solution 5 that by mass percentage, addition concentration is 15~25% in 0.5~2g cellulose paste~
10mL carries out quaternization at normal temperature, and after reacting 2~4h, adding 5~10mL concentration is 20~25% sodium chloroacetate solutions
Etherification reaction is carried out at a temperature of 40~60 DEG C, reacts 3~5h, is finally washed fiber with dehydrated alcohol at room temperature and is obtained to neutral
To carboxymethyl cellulose；
2) the n,N-Dimethylformamide DMF of two parts of 100mL, the mixed solution of second alcohol and water are configured, solution A and B solution are denoted as,
N,N-dimethylformamide DMF, second alcohol and water volume ratio be 1:1:1；Cu system metal salt is added in solution A, Cu ion is dense
Degree is 0.0043mM, and organic ligand is added in B solution, and Cu ion and organic ligand molar ratio are 1:3, are sufficiently stirred；Weigh 1
~3g carboxymethyl cellulose first impregnates 30~120min in solution A, and 30~120min, weight are then impregnated in being transferred to B solution
Complex Alternating impregnates 4~6 times；Carboxymethyl cellulose impregnates to 4 hours after the completion of dipping in 100mL methylene chloride, finally 60~
At 80 DEG C be dried in vacuo 3~5h, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose, be denoted as MOF/ fibre
Dimension；
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and weighing concentration of silver ions is 60~80mM
Ag system metal salt be added mixed solution in, be sufficiently stirred；MOF/ fiber prepared by step 2 is added to above-mentioned mixed solution
In be sufficiently impregnated 6~8h of stirring, then filter out fiber, nanometer Ag restored into load using Microwave reduction method and is dispersed in
On MOFs；Finally sample is washed with deionized 5~8 times, is filtered, forming of manufacturing paper with pulp obtains paper base filter membrane material.
2. the preparation method of fiber composite film catalyst according to claim 1, which is characterized in that the cellulose
Slurry uses cotton dissolving pulp, DQP bleached bamboo pulp or hardwood pulp, and cellulose paste disperses by slurry, and it is 2 that mass fraction, which is made,
~10% cellulose paste.
3. the preparation method of fiber composite film catalyst according to claim 1, which is characterized in that quaternization hydrogen-oxygen
The mass ratio for changing sodium and fibre stuff is 0.5~1.25:1g, and the mass ratio of sodium chloroacetate and fibre stuff is 1 in etherification reaction
~2:1g.
4. the preparation method of fiber composite film catalyst according to claim 1, which is characterized in that the N, N- bis-
Methylformamide (DMF), the volume ratio of second alcohol and water are 1:1:1, and Cu system metal salt uses copper nitrate, copper acetate, sulfuric acid
Copper or copper chloride；Organic ligand is trimesic acid or terephthalic acid (TPA)；The fiber impregnation time is 30~120min.
5. the preparation method of fiber composite film catalyst according to claim 1, which is characterized in that the Ag system gold
Belong to salt and use silver nitrate, silver sulfate or silver fluoride, concentration of silver ions is 60~80mM, 5~8h of dipping stirring after solution is added.
6. the preparation method of fiber composite film catalyst according to claim 1, which is characterized in that microwave reduction used
Method, the power of microwave reduction are 600~800w, and the recovery time is 10~20 minutes.
7. the preparation method of fiber composite film catalyst according to claim 1, which comprises the following steps:
1) cotton dissolving pulp is chosen, is dispersed by mashing, the cellulose paste that mass fraction is 4% is made；In 1g cellulose paste
Addition 5ml concentration is 15% sodium hydroxide solution, carries out quaternization at normal temperature, and after reacting 3h, adding 5ml concentration is 20%
Sodium chloroacetate solution carry out etherification reaction at 60 DEG C, react 4h, finally wash fiber into dehydrated alcohol at room temperature
Property obtains carboxymethyl cellulose；
2) N,N-dimethylformamide (DMF) of two parts of 100ml is configured, the mixed solution of second alcohol and water is denoted as solution A and B is molten
Liquid, n,N-Dimethylformamide (DMF), the volume ratio of second alcohol and water are 1:1:1；2g copper acetate is added in solution A, it is molten in B
1g trimesic acid is added in liquid, is sufficiently stirred；The carboxymethyl cellulose for weighing 2g first impregnates 30min in solution A, is then turning
It moves on to and impregnates 30min in B solution, repeat alternating impregnating 5 times；After the completion of dipping by carboxymethyl cellulose in 100ml methylene chloride
Impregnate 4 hours, be finally dried in vacuo 4h at 70 DEG C, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose,
It is denoted as MOFs/ fiber；
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and mixing is added in the silver nitrate for weighing 0.5g
In solution, it is sufficiently stirred；MOFs/ fiber prepared by step 2 is add to the above mixed solution and is sufficiently impregnated stirring 6h, so
After filter out fiber, fiber is placed under the microwave of 700w and restores 15min, nanometer Ag can restore load and be dispersed in MOF
On；It is finally washed with deionized 6 times, filters, forming of manufacturing paper with pulp obtains paper-based membrane catalysis material.
8. the preparation method of fiber composite film catalyst according to claim 1, which comprises the following steps:
1) DQP bleached bamboo pulp is chosen, is dispersed by mashing, the cellulose paste that mass fraction is 6% is made；In 0.5g slurry
Addition 8ml concentration is 20% sodium hydroxide solution, carries out quaternization at normal temperature, and after reacting 2h, adding 8ml concentration is
25% sodium chloroacetate solution carries out etherification reaction at 50 DEG C, reacts 3h, finally washs fiber extremely with dehydrated alcohol at room temperature
Neutrality obtains carboxymethyl cellulose；
2) DMF of two parts of 100ml is configured, the mixed solution of second alcohol and water is denoted as solution A and B solution, n,N-Dimethylformamide
(DMF), the volume ratio of second alcohol and water is 1:1:1；2g copper nitrate is added in solution A, 1g terephthaldehyde is added in B solution
Acid is sufficiently stirred；The carboxymethyl cellulose for weighing 1g first impregnates 60min in A liquid, then impregnates 60min in being transferred to B liquid,
It repeats alternating impregnating 6 times；Carboxymethyl cellulose is impregnated 4 hours in 100ml methylene chloride after the completion of dipping, finally at 80 DEG C
Be dried in vacuo 5h, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose, be denoted as MOFs/ fiber；
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and the silver sulfate addition mixing for weighing 1g is molten
In liquid, it is sufficiently stirred；MOFs/ fiber prepared by step 2 is add to the above mixed solution and is sufficiently impregnated stirring 8h, then
Fiber is filtered out, fiber is placed in reductase 12 0min under the microwave of 800w, nanometer Ag can restore load and be dispersed in MOFs
On；It is finally washed with deionized 5 times, filters, forming of manufacturing paper with pulp obtains paper-based membrane catalysis material.
9. the preparation method of fiber composite film catalyst according to claim 1, which comprises the following steps:
1) hardwood pulp is chosen, is dispersed by mashing, the cellulose paste that mass fraction is 10% is made；In 2g cellulose paste
The middle sodium hydroxide solution that 10ml concentration is added and is 25%, carries out quaternization at normal temperature, after reacting 4h, it is dense to add 10ml
Degree carries out etherification reaction for 25% sodium chloroacetate solution at 40 DEG C, reacts 5h, finally washs fibre with dehydrated alcohol at room temperature
Dimension to neutrality obtains carboxymethyl cellulose；
2) n,N-Dimethylformamide (DMF) of two parts of 100ml is configured, the mixed solution of second alcohol and water is denoted as solution A and B is molten
Liquid, n,N-Dimethylformamide (DMF), the volume ratio of second alcohol and water are 1:1:1；2g copper sulphate is added in solution A, it is molten in B
1g terephthalic acid (TPA) is added in liquid, is sufficiently stirred；The carboxymethyl cellulose for weighing 3g first impregnates 120min in A liquid, is then turning
It moves on in B liquid and impregnates 120min, repeat alternating impregnating 4 times；Fiber is impregnated to 4 in 100ml methylene chloride small after the completion of dipping
When, be finally dried in vacuo 3h at 60 DEG C, Cu system metal framework object MOFs can fabricated in situ on carboxymethyl cellulose, be denoted as
MOFs/ fiber；
3) mixed solution of 50ml second alcohol and water is configured, ethyl alcohol and water volume ratio are 5:1, and mixing is added in the silver fluoride for weighing 0.6g
In solution, it is sufficiently stirred；The MOFs/ fiber of step 2 step preparation is added in above-mentioned solution and is sufficiently impregnated stirring 8h, then
Fiber is filtered out, fiber is placed under the microwave of 600w and restores 10min, nanometer Ag can restore load and be dispersed in MOFs
On；Last deionized water is washed 8 times, is filtered, and forming of manufacturing paper with pulp obtains paper-based membrane catalysis material.
10. the application of fiber composite film catalyst, which is characterized in that fiber composite film catalyst to be used in catalytic degradation waste water
P-nitrophenol.
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| CN115420841B (en) * | 2022-09-29 | 2023-11-14 | 华中师范大学 | Online catalytic membrane reactor-high performance liquid chromatography combined system and preparation method and application thereof |
| CN115807333A (en) * | 2022-12-09 | 2023-03-17 | 电子科技大学 | Preparation method of photocatalytic metal organic framework composite fiber |
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