CN110681415B - Modified CNF membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof - Google Patents
Modified CNF membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof Download PDFInfo
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- CN110681415B CN110681415B CN201910954943.0A CN201910954943A CN110681415B CN 110681415 B CN110681415 B CN 110681415B CN 201910954943 A CN201910954943 A CN 201910954943A CN 110681415 B CN110681415 B CN 110681415B
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- 239000012528 membrane Substances 0.000 title claims abstract description 100
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 230000000593 degrading effect Effects 0.000 title claims abstract description 22
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 64
- 239000000835 fiber Substances 0.000 claims abstract description 60
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 230000015556 catabolic process Effects 0.000 claims abstract description 28
- 238000006731 degradation reaction Methods 0.000 claims abstract description 28
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 100
- 239000002244 precipitate Substances 0.000 claims description 61
- 238000005406 washing Methods 0.000 claims description 53
- 239000000725 suspension Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 15
- 229940043237 diethanolamine Drugs 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 14
- 238000010345 tape casting Methods 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 8
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- SWXQKHHHCFXQJF-UHFFFAOYSA-N azane;hydrogen peroxide Chemical compound [NH4+].[O-]O SWXQKHHHCFXQJF-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 60
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- 239000000706 filtrate Substances 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 18
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 13
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4007—Regeneration or reactivation of catalysts containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the technical field of nanocellulose fiber catalysts, in particular to a modified CNF membrane capable of catalytically degrading 4-nitrophenol, and a preparation method and application thereof. The modified CNF film comprises: the nano-CuO particles grow on the nano-cellulose fibers in situ, and amine groups are grafted on the surfaces of the nano-cellulose fibers. The modified CNF film has excellent catalytic degradation capability on degradable 4-nitrophenol, and can efficiently catalytically degrade the 4-nitrophenol in a short time.
Description
Technical Field
The invention relates to the technical field of nanocellulose fiber catalysts, in particular to modified nanocellulose fibers suitable for catalytic degradation of 4-nitrophenol, and a preparation method and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
4-nitrophenol is a stubborn water impurity, widely originated from coloring agent, pesticide and pharmaceutical industry, and is a toxic organic pollutant. 4-nitrophenol is converted into 4-aminophenol, so that the toxicity of the 4-nitrophenol can be reduced, and the 4-aminophenol serving as a fine organic chemical intermediate with wide application can be used for synthesizing paracetamol and the like in the medical industry and can also be used for preparing products such as a developer, an antioxidant, a petroleum additive and the like.
At present, two methods, namely a photocatalytic degradation method and a nano noble metal particle catalytic degradation method, are mainly used for the catalytic degradation of 4-nitrophenol. The photocatalytic degradation is mainly of semiconductors (e.g. nano TiO)2Nano ZnO, etc.) is irradiated by ultraviolet light with a wavelength of less than 387.5nm, electrons on the valence band are excited and jump into the conduction band, thereby generating negatively charged highly active electrons (e) on the conduction band-) And positive charge holes (h +) are left on the valence band, and under the action of an electric field, electrons and holes are separated and migrate to different parts on the surface of particles to form an oxidation-reduction system, and 4-nitrophenol is catalytically reduced as a sacrificial agent. However, the present inventors found that: the price of semiconductor materials is high, the requirements of photocatalysis on conditions are strict, the reaction is slow, and industrialization cannot be realized. The noble metal particles have small particle size and high surface atom occupancy, have unique quantum size effect, surface effect, macroscopic quantum tunneling effect and the like, generate a plurality of unique optical, electrical and catalytic properties and the like, have extremely high specific surface area and surface activity, can efficiently catalyze and degrade the 4-nitrophenol, but have high noble metal cost and low economic practicability. In addition, the catalyst in the photocatalytic degradation method and the nano noble metal particle degradation method is difficult to recover.
Disclosure of Invention
The technical problem to be solved/the objects to be achieved by the present invention include at least: (1) preparing a green and renewable catalyst capable of treating 4-nitrophenol (such as wastewater); (2) the catalytic efficiency is high; (3) the catalytic efficiency is high when the catalyst is recycled; the problems of large usage amount of chemical medicines for degrading the 4-nitrophenol, unsatisfactory treatment effect and the like in the prior method are solved.
Therefore, the invention provides a modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol, and a preparation method and application thereof; according to the invention, the nano cellulose fiber (CNF) is used as a raw material, CuO is loaded, and an amino group is grafted, so that the nano cellulose fiber has the capability of catalyzing and degrading 4-nitrophenol, is mixed with polyvinyl alcohol to form a membrane for sewage treatment, can be recycled, and can provide a new direction for industrial application of the CNF.
In order to realize the purpose, the invention discloses the following technical scheme:
firstly, a modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol is provided, which comprises: the nano-CuO particle in-situ growth method comprises nano-cellulose fibers (CNF) and nano-CuO particles, wherein the nano-CuO particles grow on the nano-cellulose fibers in situ, and the surfaces of the nano-cellulose fibers are coupled and grafted with amine groups.
Secondly, the preparation method of the modified nano cellulose fiber membrane comprises the following steps:
(1) mixing the CNF suspension and the hydrogen peroxide-ammonia water mixed solution, and uniformly stirring; centrifuging, and washing the obtained CNF to be neutral for later use;
(2) mixing the CNF obtained in the step (1) with a water-soluble copper source and an alkali liquor, and stirring and reacting at a set temperature until the CNF is black to obtain CNF @ CuO; the nano copper oxide is synthesized in a CNF aqueous suspension system, which is beneficial to reducing the aggregation of the copper oxide, and the CuO @ CNF has catalytic performance due to the CuO loading;
(3) redispersing CNF @ CuO, adding the CNF @ CuO into a silane coupling agent, reacting at a set water bath temperature, centrifuging the reaction solution after the reaction is finished, washing and collecting precipitate to obtain hydrophobic modified CNF @ CuO; the silane coupling agent is mainly grafted on the surface of the CNF for improving the hydrophobicity of the CNF, and can be coupled and grafted with glycol amine;
(4) redispersing the hydrophobically modified CNF @ CuO, adding diethanol amine, removing oxygen in a reaction system, reacting at a set water bath temperature, centrifuging the reaction solution after the reaction is finished, washing and collecting precipitate to obtain the amino grafted modified nano cellulose fiber; the catalytic performance of the glycol amine can effectively improve the catalytic performance of the composite material;
(5) and mixing the modified nano cellulose fiber with polyvinyl alcohol, and performing tape casting to form a film, thus obtaining the modified nano cellulose fiber.
In addition, a process for the catalytic degradation of 4-nitrophenol is provided: adding the modified nano cellulose fiber membrane provided by the invention into a 4-nitrophenol solution, and simultaneously adding NaBH4Stirring to obtain the product.
Compared with the prior art, the invention has the following beneficial effects:
(1) the CNF film is used as a raw material, and the modification is carried out under a water system condition, so that the CNF film has the advantages of environmental friendliness and reproducibility.
(2) The modified CNF film has excellent catalytic degradation capability on degradable 4-nitrophenol, the degradation rate can reach more than 94% when the film is used for the first time, the 4-nitrophenol can be efficiently catalytically degraded in a short time, and the dosage of the modified CNF film can be remarkably reduced compared with the dosage of the modified CNF film treated by traditional chemicals for treating the 4-nitrophenol.
(3) The modified CNF film can convert 4-nitrophenol into 4-aminophenol, not only can reduce the toxicity of the 4-nitrophenol, but also can be used as a fine organic chemical intermediate to be beneficial.
(4) The modified CNF film can be washed and recovered by deionized water, and is a clean product; and after multiple use, recovery and use, the degradation rate of the 4-nitrophenol is still kept above 85 percent.
(5) The preparation method is simple, strong in degradation capability, strong in practicability and easy to popularize.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms also are intended to include the plural forms as well, unless the context clearly indicates otherwise, and it should be further understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
As mentioned above, the combination of the green renewable materials to treat the 4-nitrophenol in the wastewater, reduce the use of chemicals, improve the treatment efficiency and the like are important ways to realize the degradation of the 4-nitrophenol. Therefore, the invention provides a modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol and a preparation method thereof.
In some typical embodiments, the CNF in the modified nano-cellulose fiber has a length of 500-2000nm and a diameter of 10-50 nm;
in some exemplary embodiments, the modified nanocellulose fiber has a mass ratio of CNF to CuO of 1: 1-2, an excess of CuO causes an increase in dispersed CuO in the CNF network structure and is lost in the washing process.
In some exemplary embodiments, the amine groups in the modified nanocellulose fibers are provided by diethanolamine.
In some exemplary embodiments, in the step (1), CNF is prepared by a sulfuric acid method and is sonicated.
In some typical embodiments, in the step (1), the CNF and the hydrogen peroxide-ammonia water mixture are added in a ratio of 1-2 g: 10 mL; preferably, the volume ratio of the hydrogen peroxide to the ammonia water mixed solution is 1: 1-2. The main purpose of adding the hydrogen peroxide-ammonia water mixed solution is to remove sulfonic acid groups attached to the surface of the CNF and increase the content of hydroxyl groups, thereby improving the surface activity of the CNF and being beneficial to the subsequent modification process.
In some exemplary embodiments, in the step (1), the water-soluble copper source includes any one of copper sulfate, copper nitrate, copper chloride, and the like.
In some exemplary embodiments, in the step (2), the alkali solution includes sodium hydroxide, ammonia water, and the like.
In some exemplary embodiments, in the step (2), the temperature is set to 60 to 90 ℃.
In some exemplary embodiments, in the step (3), the temperature of the water bath is set to 50 to 85 ℃.
In some exemplary embodiments, in the step (3), the mass ratio of CNF to silane coupling agent is 10 to 5: 1. the silane coupling agent is mainly grafted on the CNF surface for increasing its hydrophobicity, and the silane coupling agent can couple the grafted glycol amine, but more than 5: 1 can lead to the obvious increase of the hydrophobicity of the CNF, and is not beneficial to the catalytic degradation of the CNF membrane in water.
In some exemplary embodiments, in the step (3), the silane coupling agent includes: 3-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, and the like.
In some exemplary embodiments, the amount of glycol amine used in step (4) is 1 to 30wt% (relative to the absolute dry CNF mass). The main purpose of adding glycol amine is to graft a catalytically active alcohol amine group, replacing-Cl on the silane group.
Preferably, in the step (4), the amount of glycol amine is 5 to 20wt% (relative to the absolute dry mass of CNF). Further research of the invention finds that when the dosage of ethylene glycol amine is less than 5 wt%, the catalytic degradation effect of the modified CNF film on 4-nitrophenol is poor; when the dosage of the ethylene glycol amine is more than 20wt%, the catalytic degradation effect of the 4-nitrophenol is not greatly influenced by continuously increasing the dosage of the ethylene glycol amine.
In some exemplary embodiments, in the step (4), the oxygen in the reaction system is removed by continuously introducing nitrogen into the reaction system.
In some exemplary embodiments, in the step (4), the temperature of the water bath is set to 45 to 60 ℃.
In some exemplary embodiments, the method for catalytically degrading 4-nitrophenol modifies a CNF membrane with NaBH4The mass ratio of (A) to (B) is 1-10: 6, over 10: the removal rate of 6-p-4-nitrophenol is not obviously improved.
In some exemplary embodiments, the volume ratio of the modified nanocellulose fiber suspension to polyvinyl alcohol is from 2 to 4: 1.
in some exemplary embodiments, the modified CNF membrane may be recovered by washing with deionized water and reused for catalytic degradation of 4-nitrophenol.
In some exemplary embodiments, the modified nanocellulose fibers are also used in environmental, chemical, pharmaceutical fields.
The invention will now be further described with reference to specific embodiments.
Example 1
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF:
a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use.
b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral.
c) Taking out the precipitate, placing in an ultrasonic cell crusher, treating for 30min at 1200W power, homogenizing for 15min under the pressure of a first-stage valve of a high-pressure homogenizer at 80bar and the pressure of a second-stage valve at 350bar to obtain CNF suspension.
(2) Preparation of modified CNF membrane:
d) taking 10g of the CNF suspension of step c) and placing in a three-neck flask, adding 100mL of H2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in the step d) in a three-neck flask, and adding 0.2M CuSO4And 1.0M NaOH are dispersed in 100mL of deionized water and transferred into a three-neck flask, and the mixture is stirred for 4h at 60 ℃ until the solution is black, so that CNF @ CuO is obtained, wherein the mass ratio of the CNF to the CuO is 1: 1.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersed and 0.8g of 3-aminopropyltriethoxysilane was added, stirred in a water bath at 50 ℃ for 6h, washed by centrifugation until the filtrate was free of chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-APTS.
g) Taking 6g of CNF @ CuO-APTS obtained in the step f) into a three-neck flask, adding 1 wt% of diethanolamine (relative to the CNF @ CuO-APTS obtained in the step e), continuously introducing nitrogen, reacting in a water bath at 45 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) mixing the suspension of modified CNF of step g) (concentration 1.0 wt%) with polyvinyl alcohol according to volume 4: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1 mmol/L4-nitrophenol is placed in a beaker, 100mg of modified CNF membrane is added, and 600mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally recovering the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 2
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) taking 10g of the CNF suspension of step c) and placing in a three-neck flask, adding 100mLH2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in the step d) in a three-neck flask, and adding 0.2M CuSO4Dispersed with 1.0M NaOH in 100mL deionized water and transferred to a three-necked flaskAnd stirring for 4 hours at the temperature of 60 ℃ until the solution is black, wherein the obtained precipitate is CNF @ CuO, and the mass ratio of CNF to CuO is 1: 1.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersion and 0.8g of gamma-methacryloxypropyltrimethoxysilane were added, stirred in a water bath at 50 ℃ for 6h, washed with aqueous ethanol until the filtrate contained no chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-MPS.
g) Taking 6g of CNF @ CuO-MPS obtained in the step e) into a three-neck flask, adding 5 wt% of diethanolamine (relative to the CNF @ CuO-MPS obtained in the step e), continuously introducing nitrogen, reacting in a water bath at 45 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) mixing the suspension of modified CNF of step g) (concentration 1.0 wt%) with polyvinyl alcohol according to volume 4: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1 mmol/L4-nitrophenol is placed in a beaker, 100mg of modified CNF membrane is added, and 600mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 3
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) taking 10g of the CNF suspension of step c) and placing in a three-neck flask, adding 100mLH2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Get 8g of the warpPlacing the nano cellulose fiber treated in the step d) into a three-neck flask, and adding 0.2M CuSO4Dispersing the solution and 1.0M NaOH in 100mL of deionized water, transferring the solution into a three-neck flask, stirring the solution for 4 hours at 60 ℃ until the solution is black, and obtaining a precipitate, namely CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 1.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersion and 0.8g of gamma-methacryloxypropyltrimethoxysilane were added, stirred in a water bath at 50 ℃ for 6h, washed with aqueous ethanol until the filtrate contained no chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-MPS.
g) Putting 6g of CNF @ CuO-MPS into a three-neck flask, adding 5 wt% of diethanolamine (corresponding to the CNF @ CuO-MPS in the step e), continuously introducing nitrogen, reacting in a water bath at 45 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) mixing the suspension of modified CNF of step g) (concentration 1.2 wt%) with polyvinyl alcohol according to volume 4: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1 mmol/L4-nitrophenol is placed in a beaker, 100mg of modified CNF membrane is added, and 600mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 4
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) 20g of the above suspension of nanocellulose filaments was taken in a three-necked flask and 100mLH added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 2) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in step d) in a three-neck flask, 0.2M CuCl2And 1.0M NaOH are dispersed in 100mL of deionized water and transferred to a three-neck flask, and the mixture is stirred for 4 hours at 70 ℃ until the solution is black, and the obtained precipitate is CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 2.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersion and 1.0g of gamma- (2, 3-propylene oxide) propyltrimethoxysilane were added, stirred in a water bath at 60 ℃ for 6h, washed with aqueous ethanol until the filtrate was free of chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-EPPM.
g) Taking 6g of CNF @ CuO-EPPM, adding 10 wt% of diethanolamine (corresponding to the CNF @ CuO-EPPM in the step e) into a three-neck flask, continuously introducing nitrogen, reacting in a water bath at 50 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) the suspension of the modified CNF membrane (concentration 1.5 wt%) was mixed with polyvinyl alcohol according to a volume 3: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1 mmol/L4-nitrophenol is placed in a beaker, 100mg of modified CNF membrane is added, and 200mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 5
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) 20g of the CNF suspension from step c) were placed in a three-necked flask and 100mLH was added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 2) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in step d) in a three-neck flask, 0.2M CuCl2And 1.0M NaOH are dispersed in 100mL of deionized water and transferred to a three-neck flask, and the mixture is stirred for 4 hours at 70 ℃ until the solution is black, and the obtained precipitate is CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 2.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersion and 1.0g of 3-aminopropyltriethoxysilane was added, stirred in a water bath at 60 ℃ for 6h, washed with aqueous ethanol until the filtrate was free of chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-APTS.
g) Taking 6g of CNF @ CuO-APTS obtained in the step f) into a three-neck flask, adding 10 wt% of diethanolamine (relative to the CNF @ CuO-APTS obtained in the step e), continuously introducing nitrogen, reacting in a water bath at 50 ℃ for 12 hours, centrifugally washing with water ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) mixing the suspension of modified CNF of step g) (concentration 1.0 wt%) with polyvinyl alcohol according to a volume 3: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1 mmol/L4-nitrophenol is placed in a beaker, 200mg of modified CNF membrane is added, and 200mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 6
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) 20g of the CNF suspension from step c) were placed in a three-necked flask and 100mLH was added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 2) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in step d) in a three-neck flask, 0.2M CuCl2And 1.0M NaOH are dispersed in 100mL of deionized water and transferred to a three-neck flask, and the mixture is stirred for 4 hours at 70 ℃ until the solution is black, and the obtained precipitate is CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 2.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersion and 1.0g of gamma-methacryloxypropyltrimethoxysilane were added, stirred in a water bath at 60 ℃ for 6h, washed with aqueous ethanol until the filtrate contained no chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-MPS.
g) Putting 6g of CNF @ CuO-MPS into a three-neck flask, adding 10 wt% of diethanolamine (corresponding to the CNF @ CuO-MPS in the step e), continuously introducing nitrogen, reacting in a water bath at 50 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) mixing the suspension of modified CNF of step g) (concentration 1.0 wt%) with polyvinyl alcohol according to a volume 3: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1 mmol/L4-nitrophenol is placed in a beaker, 300mg of modified CNF membrane is added, and 200mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 7
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) taking 10g of the CNF suspension of step c) and placing in a three-neck flask, adding 100mLH2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in step d) in a three-neck flask, 0.2M Cu (NO)3)2Dispersing the precipitate and 1.0M NaOH in 100mL of deionized water, transferring the mixture into a three-neck flask, stirring the mixture for 4 hours at 80 ℃ until the solution is black, and obtaining a precipitate, namely CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 1.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersion and 1.3g of 3-aminopropyltriethoxysilane were added, stirred in a water bath at 70 ℃ for 6h, washed centrifugally with aqueous ethanol until the filtrate was free of chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-APTS.
g) Taking 6g of CNF @ CuO-APTS obtained in the step f) to be put in a three-neck flask, adding 15 wt% of diethanolamine (relative to the CNF @ CuO-APTS obtained in the step e), continuously introducing nitrogen, reacting in a water bath at 55 ℃ for 12 hours, centrifugally washing with water ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) mixing the suspension of modified CNF of step g) (concentration 1.0 wt%) with polyvinyl alcohol according to volume 2: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1 mmol/L4-nitrophenol is placed in a beaker, 400mg of modified CNF membrane is added, and 100mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. Deionized waterAnd washing and recovering the modified CNF membrane for reuse.
Example 8
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) taking 10g of the CNF suspension of step c) and placing in a three-neck flask, adding 100mLH2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in step d) in a three-neck flask, 0.2M Cu (NO)3)2With 1.0M NH3·H2Dispersing O in 100mL of deionized water, transferring the deionized water into a three-neck flask, stirring the mixture for 4 hours at 80 ℃ until the solution is black, and obtaining a precipitate, namely CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 1.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redisperse and add 1.3g gamma-methacryloxypropyltrimethoxysilane, stir in a 70 ℃ water bath for 6h, wash with aqueous ethanol until the filtrate is free of chloride ions, collect the precipitate and measure the moisture. The obtained precipitate is CNF @ CuO-MPS.
g) Putting 6g of CNF @ CuO-MPS into a three-neck flask, adding 15 wt% of diethanolamine (corresponding to the CNF @ CuO-MPS in the step e), continuously introducing nitrogen, reacting in a water bath at 55 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain modified CNF suspension;
h) mixing the suspension of modified CNF of step g) (concentration 1.5 wt%) with polyvinyl alcohol according to volume 2: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 1.5 mmol/L4-nitrophenol is placed in a beaker, 200mg of modified CNF membrane is added, and 100mg of NaBH is added at the same time4Mechanically stirring for 5min, and separatingThe modified CNF membrane was recovered by heart washing, and the supernatant liquid was collected and scanned with an ultraviolet-visible spectrophotometer, and the absorbance at 400nm was recorded to calculate its concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 9
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) taking 10g of the CNF suspension of step c) and placing in a three-neck flask, adding 100mLH2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in step d) in a three-neck flask, 0.2M Cu (NO)3)2With 1.0M NH3·H2Dispersing O in 100mL of deionized water, transferring the deionized water into a three-neck flask, stirring the mixture for 4 hours at 80 ℃ until the solution is black, and obtaining a precipitate, namely CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 1.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersion was carried out, 1.3g of 3-aminopropyltriethoxysilane was added, stirred in a water bath at 70 ℃ for 6h, washed by aqueous ethanol centrifugation until the filtrate was free of chloride ions, the precipitate was collected and the moisture was measured. The obtained precipitate is CNF @ CuO-APTS.
g) Taking 6g of CNF @ CuO-APTS into a three-neck flask, adding 15 wt% of diethanolamine (relative to CNF @ CuO-APTS in the step e), continuously introducing nitrogen, reacting in a water bath at 55 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain a modified CNF suspension membrane;
h) the suspension of the modified CNF membrane (concentration 1.0 wt%) was mixed with polyvinyl alcohol according to a volume 2: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
taking 50mL of 2 mmol/L4-nitrophenol and placing in a beaker, adding 200mg of modified CNF membrane and simultaneously adding 100mg of NaBH4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 10
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) 20g of the CNF suspension from step c) were placed in a three-necked flask and 100mL of H were added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 2) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in the step d) in a three-neck flask, and adding 0.2M CuSO4With 1.0M NH3·H2Dispersing O in 100mL of deionized water, transferring the deionized water into a three-neck flask, stirring the mixture for 4 hours at 90 ℃ until the solution is black, and obtaining a precipitate, namely CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 2.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redisperse and add 1.6g gamma-methacryloxypropyltrimethoxysilane, stir in a water bath at 85 ℃ for 6h, wash with aqueous ethanol until the filtrate is free of chloride ions, collect the precipitate and measure the moisture. The obtained precipitate is CNF @ CuO-MPS.
g) Putting 6g of CNF @ CuO-MPS into a three-neck flask, adding 20wt% of diethanolamine (corresponding to the CNF @ CuO-MPS in the step e), continuously introducing nitrogen, reacting in a water bath at 60 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain a modified CNF suspension membrane;
h) the suspension of the modified CNF membrane (concentration 1.0 wt%) was mixed with polyvinyl alcohol according to a volume 2: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 2.5 mmol/L4-nitrophenol is placed in a beaker, 200mg of modified CNF membrane is added, and 60mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
Example 11
1. A modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following specific steps:
(1) preparation of CNF: the same as in example 1.
(2) Preparation of modified CNF membrane:
d) 20g of the CNF suspension from step c) were placed in a three-necked flask and 100mL of H were added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 2) at room temperature for 1h, centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture.
e) Taking 8g of CNF treated in the step d) in a three-neck flask, and adding 0.2M CuSO4With 1.0M NH3·H2Dispersing O in 100mL of deionized water, transferring the deionized water into a three-neck flask, stirring the mixture for 4 hours at 90 ℃ until the solution is black, and obtaining a precipitate, namely CNF @ CuO, wherein the mass ratio of the CNF to the CuO is 1: 2.
f) taking 8g of CNF @ CuO in the step e), adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3) redispersed and 1.6g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane added, stirred in a water bath at 85 ℃ for 6h, washed with aqueous ethanol until the filtrate is free of chloride ions by centrifugation, the precipitate collected and the moisture measured. The obtained precipitate is CNF @ CuO-EPPM.
g) Putting 6g of CNF @ CuO-EPPM into a three-neck flask, adding 30wt% of diethanolamine (relative to CNF @ CuO-EPPM in the step e), continuously introducing nitrogen, reacting in a water bath at 60 ℃ for 12 hours, centrifugally washing with water and ethanol until filtrate does not contain chloride ions, and collecting precipitate to obtain a modified CNF suspension membrane;
h) the suspension of the modified CNF membrane (concentration 1.0 wt%) was mixed with polyvinyl alcohol according to a volume 2: 1, mixing, and performing tape casting to form a film.
2. And (3) testing the catalytic degradation of the modified CNF membrane by 4-nitrophenol:
50mL of 3 mmol/L4-nitrophenol is placed in a beaker, 200mg of modified CNF membrane is added, and 60mg of NaBH is added at the same time4Mechanically stirring for 5min, centrifugally washing to recover the modified CNF film, collecting the upper layer liquid, scanning with an ultraviolet-visible spectrophotometer, recording the absorption rate at 400nm, and calculating the concentration. And washing with deionized water to recover the modified CNF membrane for reuse.
And (3) performance testing:
the concentration of the filtrate after the 4-nitrophenol treatment of the modified nanocellulose filaments prepared in examples 1 to 11 was determined using the concentration of 4-nitrophenol in the filtrate as an index for performance testing. The test method comprises the following steps: 0.005g/L, 0.001g/L, 0.0015g/L, 0.002g/L and 0.0025g/L of 4-nitrophenol standard samples are respectively prepared, placed in an ultraviolet visible spectrophotometer to measure absorbance, and a standard curve is determined, as shown in Table 1.
The filtrates were separately placed in an ultraviolet-visible spectrophotometer to measure absorbance, and the concentrations thereof were calculated from the standard curves, with the test results shown in tables 2 and 3.
TABLE 14 ultraviolet visible Absorbance of Nitrophenol standards
| Concentration of 4-nitrophenol/g/L | 0.0005 | 0.001 | 0.0015 | 0.002 | 0.0025 |
| absorbance/T% | 0.02286 | 0.03559 | 0.04033 | 0.04875 | 0.05715 |
According to calculation, the standard curve is 16.827x +0.0151 y; wherein x is the concentration of 4-nitrophenol, g/L; and y is the absorbance of ultraviolet and visible light, T%.
TABLE 2 removal of 4-nitrophenol from modified nanocellulose filaments prepared in examples 1-5
| Example number | 1 | 2 | 3 | 4 | 5 |
| absorbance/T% | 0.14632 | 0.12931 | 0.07269 | 0.06153 | 0.05425 |
| concentration/mmol/L | 0.05651 | 0.04883 | 0.02462 | 0.01985 | 0.01674 |
| Removal rate/%) | 94.35 | 95.12 | 97.54 | 98.02 | 98.33 |
| Number of times of reuse | 25 | 25 | 25 | 25 | 25 |
| Removal rate after recycling/%) | 85.08 | 85.46 | 86.12 | 88.15 | 88.67 |
Table 3 removal rate of modified nanocellulose filaments prepared in examples 6 to 11 after 4-nitrophenol
As can be seen from Table 2, after CNF is modified by the method of the invention, 4-nitrophenol can be efficiently catalytically degraded in a short time, and the obtained product still has excellent 4-nitrophenol removal capability after being deionized and washed for multiple times.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (25)
1. Modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol, which is characterized by comprising: the nano-CuO particles grow on the nano-cellulose fibers in situ, and the surfaces of the nano-cellulose fibers are coupled and grafted with amine groups;
the preparation method of the modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol comprises the following steps:
(1) mixing the CNF suspension and the hydrogen peroxide-ammonia water mixed solution, and uniformly stirring; centrifuging, and washing the obtained CNF to be neutral for later use;
(2) mixing the CNF obtained in the step (1) with a water-soluble copper source and an alkali liquor, and stirring and reacting at a set temperature until the CNF is black to obtain CNF @ CuO;
(3) redispersing CNF @ CuO, adding the CNF @ CuO into a silane coupling agent, reacting at a set water bath temperature, centrifuging the reaction solution after the reaction is finished, washing and collecting precipitate to obtain hydrophobic modified CNF @ CuO;
(4) redispersing the hydrophobically modified CNF @ CuO, adding diethanol amine, removing oxygen in a reaction system, reacting at a set water bath temperature, centrifuging the reaction solution after the reaction is finished, washing and collecting precipitate to obtain the amino grafted modified nano cellulose fiber;
(5) and mixing the modified nano cellulose fiber with polyvinyl alcohol, and performing tape casting to form a film, thus obtaining the modified nano cellulose fiber.
2. The modified nanocellulose fiber membrane of claim 1, wherein a mass ratio of CNF, CuO is 1: 1-2.
3. The modified nanocellulose fiber membrane of claim 1, wherein said amine groups of said modified nanocellulose fibers are provided by diethanolamine.
4. The modified nanocellulose fiber membrane of any of claims 1-3, wherein said CNF has a length of 500-2000nm and a diameter of 10-50 nm.
5. The modified nanocellulose fiber membrane of claim 1, wherein in step (1), CNF is prepared by sulfuric acid process and sonicated.
6. The modified nanocellulose fiber membrane of claim 1, wherein in step (1), the addition ratio of CNF and hydrogen peroxide-ammonia water mixture is 1-2 g: 10 mL.
7. The modified nanocellulose fiber membrane of claim 6, wherein a volume ratio of said hydrogen peroxide-ammonia water mixture is 1: 1-2.
8. The modified nanocellulose fiber membrane of claim 1, wherein in step (1), the water-soluble copper source comprises any one of copper sulfate, copper nitrate, copper chloride, and the like.
9. The modified nanocellulose fiber membrane of claim 1, wherein in step (2), said alkali solution is sodium hydroxide or ammonia.
10. The modified nanocellulose fiber membrane of claim 1, wherein in step (2), the set temperature is from 60 ℃ to 90 ℃.
11. The modified nanocellulose fiber membrane of claim 1, wherein in step (3), a water bath temperature is set to 50-85 ℃.
12. The modified nanocellulose fiber membrane of claim 1, wherein in step (3), the mass ratio of CNF to silane coupling agent is 10-5: 1.
13. the modified nanocellulose fiber membrane of claim 1, wherein in step (3), the silane coupling agent comprises: 3-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, and the like.
14. The modified nanocellulose fiber membrane of claim 1, wherein in said step (4), said means for removing oxygen from the reaction system comprises continuously introducing nitrogen gas into the reaction system.
15. The modified nanocellulose fiber membrane of claim 1, wherein in step (4), glycol amine is used in an amount of 1-30wt% relative to oven dried CNF mass.
16. The modified nanocellulose fiber membrane of claim 15, wherein in step (4), glycol amine is used in an amount of 5-20wt% relative to oven dried CNF mass.
17. The modified nanocellulose fiber membrane of claim 1, wherein in step (4), a water bath temperature is set to 45-60 ℃.
18. The modified nanocellulose fiber membrane of claim 1, further comprising the step of drying the precipitate collected from the washing of step (4).
19. The modified nanocellulose fiber membrane of claim 18, wherein said drying temperature is 40-65 ℃.
20. The modified nanocellulose fiber membrane of claim 1, wherein in step (4), the volume ratio of modified nanocellulose fiber suspension to polyvinyl alcohol is from 2 to 4: 1.
21. a method for catalytic degradation of 4-nitrophenol: characterized in that the modified nanocellulose fiber membrane of any one of claims 1 to 20 is added to a 4-nitrophenol solution, while NaBH is added4Stirring to obtain the product.
22. The method of claim 21, wherein the modified nanocellulose fiber is reacted with NaBH4The mass ratio of (A) to (B) is 1-10: 6.
23. recovering the modified nanocellulose fiber membrane of any one of claims 1-20 by centrifugation.
24. The recovery of the modified nanocellulose fiber membrane of any of claims 1-20 by centrifugation as claimed in claim 23, for catalytic degradation of 4-nitrophenol after recovery.
25. Use of the modified nanocellulose fiber membrane of any one of claims 1 to 20 in environmental, chemical, medical fields.
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