WO2021068449A1 - Modified cnf membrane capable of catalytically degrading 4-nitrophenol, preparation method therefor and application thereof - Google Patents

Modified cnf membrane capable of catalytically degrading 4-nitrophenol, preparation method therefor and application thereof Download PDF

Info

Publication number
WO2021068449A1
WO2021068449A1 PCT/CN2020/076726 CN2020076726W WO2021068449A1 WO 2021068449 A1 WO2021068449 A1 WO 2021068449A1 CN 2020076726 W CN2020076726 W CN 2020076726W WO 2021068449 A1 WO2021068449 A1 WO 2021068449A1
Authority
WO
WIPO (PCT)
Prior art keywords
cnf
modified
preparation
nitrophenol
cuo
Prior art date
Application number
PCT/CN2020/076726
Other languages
French (fr)
Chinese (zh)
Inventor
林兆云
杨桂花
陈嘉川
和铭
戢德贤
Original Assignee
齐鲁工业大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 齐鲁工业大学 filed Critical 齐鲁工业大学
Priority to JP2021517357A priority Critical patent/JP7132663B2/en
Publication of WO2021068449A1 publication Critical patent/WO2021068449A1/en

Links

Classifications

    • 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
    • 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

Definitions

  • the invention relates to the technical field of nano cellulose fiber catalysts, in particular to a modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol, and a preparation method and application thereof.
  • 4-Nitrophenol is a stubborn water impurity, widely derived from dyes, pesticides and pharmaceutical industries, and is a toxic organic pollutant.
  • the conversion of 4-nitrophenol to 4-aminophenol can not only reduce the toxicity of 4-nitrophenol, but also 4-aminophenol, as a fine organic chemical intermediate with a wide range of applications, can be used in the pharmaceutical industry to synthesize paracetamol, etc. It can also be used to prepare products such as developers, antioxidants and petroleum additives.
  • Photocatalytic degradation is mainly when semiconductors (such as nano TiO 2 , nano ZnO, etc.) are irradiated by ultraviolet light with a wavelength of less than 387.5 nm, the electrons in the valence band are excited, and the transition enters the conduction band, thus generating negative charge on the conduction band electronic high activity (E -), leaving a hole in the valence band of positively charged (h +), under the action of the electric field, electrons and holes are separated and migrate to different parts of the surface of the particle, form an oxidation - reduction
  • 4-nitrophenol is used as a sacrificial agent to be catalytically reduced.
  • the technical problems to be solved/objectives achieved by the present invention include at least: (1) Preparation of a green and renewable catalyst capable of treating 4-nitrophenol (such as in wastewater); (2) High catalytic efficiency; (3) Recycling The catalytic efficiency is high; in order to reduce the problem of large usage of the degrading 4-nitrophenol chemicals in the existing method, and the unsatisfactory treatment effect.
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol and a preparation method and application thereof; the present invention uses nano cellulose fibers (CNF) as raw materials, and nano CuO particles are grown in situ On the nano-cellulose fiber, and the surface of the nano-cellulose fiber is coupled and grafted with amine groups, so that it has the ability to catalyze the degradation of 4-nitrophenol, and is mixed with polyvinyl alcohol to form a film for sewage treatment, and it can be recycled , Which can provide a new direction for the industrial application of CNF.
  • CNF nano cellulose fibers
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, comprising: nano cellulose fibers (CNF) and nano CuO particles, the nano CuO particles being grown in situ on the nano cellulose fibers , And the surface of the nanocellulose fiber is coupled and grafted with an amine group; the amine group is an alcohol amine group.
  • CNF nano cellulose fibers
  • nano CuO particles being grown in situ on the nano cellulose fibers
  • the surface of the nanocellulose fiber is coupled and grafted with an amine group; the amine group is an alcohol amine group.
  • the mass ratio of the CNF and the nano CuO particles is 1:1-2.
  • the amine group in the nanocellulose fiber is provided by glycol amine.
  • the CNF has a length of 500-2000 nm and a diameter of 10-50 nm.
  • the present invention also provides a method for preparing the above-mentioned modified nano-cellulose fiber membrane, which includes the following steps:
  • step (2) After mixing the CNF treated in step (1), the water-soluble copper source, and the lye, the reaction is carried out under stirring conditions until black appears to obtain CNF@CuO;
  • a suspension of CNF is prepared by a sulfuric acid method, and ultrasonic treatment is performed.
  • the addition ratio of the CNF suspension and the hydrogen peroxide-ammonia mixed liquid is 1 to 2 g: 10 mL.
  • the mass ratio of the two in the hydrogen peroxide-ammonia mixture is 1:1-2.
  • the water-soluble copper source includes any one of copper sulfate, copper nitrate and copper chloride.
  • the lye is an aqueous sodium hydroxide solution or ammonia water.
  • the stirring temperature is 60-90°C.
  • the temperature of the water bath is 50-85°C.
  • the mass ratio of CNF@CuO and the silane coupling agent is 10-5:1.
  • the silane coupling agent includes 3-aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane and ⁇ -(2,3-cyclic Any one of oxypropoxy)propyltrimethoxysilane.
  • the method for removing oxygen in the reaction system is to continuously pass nitrogen into the reaction system.
  • the amount of glycol amine is 1-30 wt%.
  • the amount of glycol amine is 5-20 wt%.
  • the temperature of the water bath is 45-60°C.
  • the volume ratio of the modified nanocellulose fiber suspension grafted with amine groups to the polyvinyl alcohol is 2 to 4:1.
  • the concentration of the modified nanocellulose fiber suspension grafted with amine groups is 1.0 wt%, 1.2 wt% or 1.5 wt%.
  • the present invention also provides a method for catalytic degradation of 4-nitrophenol: adding the modified nano cellulose fiber membrane to the 4-nitrophenol solution, and at the same time adding NaBH 4 for stirring, to catalytically degrade the 4-nitrophenol. ⁇ phenol.
  • the mass ratio of the modified nanocellulose fiber membrane to NaBH 4 is 1-10:6.
  • the modified nanocellulose fiber membrane is recovered by centrifugal separation.
  • the modified nano cellulose membrane obtained after the recovery is used to catalyze the degradation of 4-nitrophenol.
  • the invention also provides the application of the modified nano cellulose fiber in the fields of environment, chemical industry and medicine.
  • the present invention has achieved the following beneficial effects:
  • the present invention uses CNF as a raw material, and the modification is carried out under water system conditions, so that it has the advantages of green, environmental protection and renewable.
  • the modified CNF membrane of the present invention has excellent catalytic degradation ability for degradable 4-nitrophenol, the degradation rate can reach more than 94% when used for the first time, and it can efficiently catalyze and degrade 4-nitrophenol in a short time.
  • the high-efficiency catalytic degradation ability of the present invention enables the modified CNF membrane of the present invention to significantly reduce the dosage compared with the traditional chemical treatment of 4-nitrophenol.
  • the modified CNF membrane of the present invention can convert 4-nitrophenol into 4-aminophenol, not only can reduce the toxicity of 4-nitrophenol, but also 4-aminophenol can be used as a fine organic chemical intermediate.
  • the modified CNF membrane of the present invention can be recovered by washing with deionized water, which is a clean product; and after multiple use-recovery-use, the degradation rate of 4-nitrophenol still remains above 85% .
  • the preparation method of the present invention is simple, has strong degradation ability, strong practicability, and is easy to popularize.
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol and a preparation method thereof.
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, comprising: nano cellulose fibers and nano CuO particles, the nano CuO particles are grown in situ on the nano cellulose fibers, and The surface of the nano cellulose fiber is coupled and grafted with an amine group.
  • the CNF in the modified nanocellulose fiber membrane has a length of 500-2000 nm and a diameter of 10-50 nm;
  • the mass ratio of CNF and nano CuO particles in the modified nanocellulose fiber membrane is 1:1 to 2, and an excessive amount of nano CuO particles will cause nano CuO particles dispersed in the CNF network structure Increase and loss in the washing process.
  • the amine group in the modified nanocellulose fiber membrane is provided by glycol amine.
  • the present invention also provides a method for preparing the modified nanocellulose fiber membrane, which is characterized in that it comprises the following steps:
  • step (2) After mixing the nanocellulose fibers treated in step (1), the water-soluble copper source and the lye, the reaction is carried out under stirring conditions until black appears, and CNF@CuO is obtained;
  • a suspension of CNF is prepared by a sulfuric acid method, and ultrasonic treatment is performed.
  • the addition ratio of the CNF suspension and the hydrogen peroxide-ammonia mixed liquid is 1 to 2 g: 10 mL.
  • the mass ratio of the two in the hydrogen peroxide ammonia water mixture is 1:1-2.
  • the main purpose of adding the hydrogen peroxide-ammonia mixture is to remove the sulfonic acid groups attached to the surface of the CNF and increase the hydroxyl content, thereby increasing the surface activity of the CNF, which is beneficial to the subsequent modification process.
  • the water-soluble copper source includes copper sulfate, copper nitrate or copper chloride.
  • the lye in the step (2), is an aqueous sodium hydroxide solution or ammonia water.
  • the stirring temperature is 60-90°C.
  • the temperature of the water bath is 50-85°C.
  • the mass ratio of CNF@CuO and the silane coupling agent is 10-5:1.
  • the silane coupling agent is mainly grafted on the surface of CNF to improve its hydrophobicity, and the silane coupling agent can be coupled and grafted with glycol amine, but the mass ratio of CNF@CuO and silane coupling agent exceeding 5:1 will cause The hydrophobicity of CNF is obviously increased, which is not conducive to the catalytic degradation of modified CNF membrane in water.
  • the silane coupling agent includes 3-aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane and ⁇ -(2 Any one of ,3-glycidoxy)propyltrimethoxysilane.
  • the method for removing oxygen in the reaction system is to continuously pass nitrogen into the reaction system.
  • the amount of the glycol amine is 1-30 wt%.
  • the main purpose of adding glycol amine is to graft the catalytically active alcohol amine group to replace -Cl on the silane group.
  • the amount of the glycol amine is 5-20 wt%. Further research of the present invention found that when the amount of glycolamine is less than 5wt%, the modified CNF membrane has a poor catalytic degradation effect on 4-nitrophenol; when the amount of glycolamine is greater than 20wt%, continue to increase the amount of glycol amine The amount of amine has little effect on the catalytic degradation of 4-nitrophenol.
  • the temperature of the water bath is 45-60°C.
  • the volume ratio of the modified nanocellulose fiber suspension grafted with amine groups to the polyvinyl alcohol is 2 to 4:1.
  • the concentration of the modified nanocellulose fiber suspension grafted with amine groups is 1.0 wt%, 1.2 wt%, or 1.5 wt%.
  • the present invention also provides a method for catalytic degradation of 4-nitrophenol: adding the modified nano cellulose fiber membrane to the 4-nitrophenol solution, and at the same time adding NaBH 4 for stirring, to catalytically degrade the 4-nitrophenol. ⁇ phenol.
  • the mass ratio of the modified CNF membrane to NaBH 4 in the method for catalytic degradation of 4-nitrophenol is 1-10:6, and the removal rate of 4-nitrophenol is improved by more than 10:6. Not obvious.
  • the modified nanocellulose membrane can be recovered by centrifugal separation; or the modified CNF membrane can be recovered by washing with deionized water and reused for 4-nitro Catalytic degradation of phenol.
  • the invention also provides the application of the modified nano cellulose fiber in the fields of environment, chemical industry and medicine.
  • a modified nano-cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e) Take 8g of CNF treated in step d) in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask, stir at 60°C for 4h until the solution turns black. Get CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step f) Take 6g of CNF@CuO-APTS of step f) in a three-necked flask, add 1wt% glycol amine (relative to CNF@CuO-APTS of step f)), and continue to pour in nitrogen, and react in a 45°C water bath 12h, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain the modified CNF suspension;
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration.
  • the modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e) Take 8g of CNF treated in step d) in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask, stir at 60°C for 4h until the solution turns black.
  • the obtained precipitate is CNF@CuO, and the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and apply it to UV-visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e Take 8g of the nanocellulose fiber treated in step d) and place it in a three-necked flask. Disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 60°C for 4h. The solution is black, and the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.2 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and apply it to UV-visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step e Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol into a beaker, add 100mg of modified CNF membrane, and at the same time add 200mg of NaBH 4 , mechanically stir for 5 minutes, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 20g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 2) at room temperature with mechanical stirring IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol in a volume of 3:1, and cast into a film to obtain.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 200mg of NaBH 4 at the same time, mechanically stir for 5 min, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy in UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration.
  • the modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 20g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 2) at room temperature with mechanical stirring IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol in a volume of 3:1, and cast into a film to obtain.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask. Disperse 0.2M Cu(NO 3 ) 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 80°C for 4h Until the solution turns black, the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 2:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 400mg of modified CNF membrane and 100mg of NaBH 4 at the same time, mechanically stir for 5 min, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M Cu(NO 3 ) 2 and 1.0M NH 3 ⁇ H 2 O in 100 mL deionized water and transfer to the three-necked flask, Stir at 80°C for 4h until the solution turns black.
  • the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.5 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 2:1, and cast into a film to obtain.
  • modified CNF membrane Take 50mL of 1.5mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 100mg of NaBH 4 at the same time, mechanically stir for 5min, centrifuge and wash to recover the modified CNF membrane, and collect the upper layer liquid and apply it to ultraviolet visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M Cu(NO 3 ) 2 and 1.0M NH 3 ⁇ H 2 O in 100 mL deionized water and transfer to the three-necked flask, Stir at 80°C for 4h until the solution turns black.
  • the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step d) Take 20g of the CNF suspension of step c) and place it in a three-necked flask, add 100 mL of a mixture of H 2 O 2 and NH 3 ⁇ H 2 O (mass ratio 1:2), mechanically stir for 1 hour at room temperature, deionized water Centrifuge and wash until neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NH 3 ⁇ H 2 O in 100mL deionized water and transfer to the three-necked flask, stir at 90 °C 4h until the solution turns black, the precipitate obtained is CNF@CuO, and the mass ratio of CNF to CuO is 1:2.
  • modified CNF membrane Take 50mL of 2.5mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 60mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper layer liquid and apply it to ultraviolet visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step d) Take 20g of the CNF suspension of step c) and place it in a three-necked flask, add 100 mL of a mixture of H 2 O 2 and NH 3 ⁇ H 2 O (mass ratio 1:2), mechanically stir for 1 hour at room temperature, deionized water Centrifuge and wash until neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF treated in step d) and place it in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NH 3 ⁇ H 2 O in 100 mL of deionized water and transfer to the three-necked flask, stir at 90°C for 4h Until the solution turns black, the precipitate obtained is CNF@CuO, and the mass ratio of CNF to CuO is 1:2.
  • modified CNF membrane Place 50mL of 3mmol/L 4-nitrophenol in a beaker, add 200mg of modified CNF membrane and 60mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration.
  • the modified CNF membrane is recovered by washing with deionized water and reused.
  • the concentration of 4-nitrophenol in the filtrate after the 4-nitrophenol was treated with the modified nanocellulose filaments prepared in Examples 1-11 was measured.
  • the test method is: configure the 4-nitrophenol standard samples of 0.005g/L, 0.001g/L, 0.0015g/L, 0.002g/L, 0.0025g/L, and place them in an ultraviolet-visible spectrophotometer to measure the absorbance. And determine the standard curve, as shown in Table 1.
  • 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 Reuse times 25 25 25 25 25 Removal rate after reuse/% 85.08 85.46 86.12 88.15 88.67
  • Example number 6 7 8 9 10 11 Absorbance/T% 0.03260 0.01611 0.06780 0.11058 0.25929 0.36335 Concentration/mmol/L 0.00748 0.00443 0.02253 0.04082 0.10440 0.14889 Removal rate/% 99.26 99.56 98.50 97.96 95.83 95.04 Reuse times 25 25 25 25 25 25 25 25 Removal rate after reuse/% 89.88 90.12 89.75 89.53 89.42 89.13

Abstract

The present invention relates to the technical field of cellulose nanofiber membrane catalysts, and relates in particular to a modified CNF membrane capable of catalytically degrading 4-nitrophenol, a preparation method therefor and an application thereof. The modified CNF membrane comprises: cellulose nanofibers and nano CuO particles, the nano CuO particles being grown in situ on the cellulose nanofibers, and the surfaces of the cellulose nanofibers being grafted with amine groups. The modified CNF membrane of the present invention has excellent catalytic degradation capabilities for degradable 4-nitrophenol, and may efficiently catalytically degrade 4-nitrophenol within a short period of time.

Description

能够催化降解4-硝基苯酚的改性CNF膜及其制备方法和应用Modified CNF membrane capable of catalytically degrading 4-nitrophenol, and preparation method and application thereof
本申请要求于2019年10月09日提交中国专利局、申请号为CN201910954943.0、发明名称为“能够催化降解4-硝基苯酚的改性CNF膜及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requires a Chinese patent application to be submitted to the Chinese Patent Office on October 9, 2019, with the application number CN201910954943.0 and the title of the invention "modified CNF membrane capable of catalytic degradation of 4-nitrophenol and its preparation method and application" The priority of, the entire content of which is incorporated in this application by reference.
技术领域Technical field
本发明涉及纳米纤维素纤维催化剂技术领域，尤其涉及一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜及其制备方法和应用。The invention relates to the technical field of nano cellulose fiber catalysts, in particular to a modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol, and a preparation method and application thereof.
背景技术Background technique
本发明背景技术中公开的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。The information disclosed in the background of the present invention is only intended to increase the understanding of the overall background of the present invention, and is not necessarily regarded as an acknowledgement or any form of suggestion that the information constitutes the prior art known to those of ordinary skill in the art.
4-硝基苯酚是一种顽固的水杂质，广泛来源于染色剂、农药和制药行业，是一种有毒有机污染物。将4-硝基苯酚转化成4-氨基苯酚不仅可以降低4-硝基苯酚的毒性，而且4-氨基苯酚作为一种应用较广泛的精细有机化工中间体，在医药工业可用于合成扑热息痛等，也可用于制备显影剂、抗氧剂和石油添加剂等产品。4-Nitrophenol is a stubborn water impurity, widely derived from dyes, pesticides and pharmaceutical industries, and is a toxic organic pollutant. The conversion of 4-nitrophenol to 4-aminophenol can not only reduce the toxicity of 4-nitrophenol, but also 4-aminophenol, as a fine organic chemical intermediate with a wide range of applications, can be used in the pharmaceutical industry to synthesize paracetamol, etc. It can also be used to prepare products such as developers, antioxidants and petroleum additives.
目前，对于4-硝基苯酚的催化降解主要有光催化降解法和纳米贵金属颗粒催化降解法两种方法。光催化降解主要是当半导体(例如纳米TiO 2、纳米ZnO等)受到波长小于387.5nm的紫外光照射时，其价带上的电子被激发，跃迁进入导带，因而在导带上产生带负电的高活性电子(e -)，在价带上留下带正电荷的空穴(h +)，在电场的作用下，电子和空穴分离并迁移到粒子表面的不同部位，形成氧化-还原体系，4-硝基苯酚作为牺牲剂被催化还原。然而，半导体材料价格较高，且光催化对条件要求较为严格，反应较慢，不可工业化。贵金属颗粒粒径较小，表面原子占有比较高，具有独特的量子尺寸效应、表面效应以及宏观量子隧道效应等使其产生了许多特有的光学、电学、催化性能等，具有极高的比表面积和表面活性，可高效催化降解4-硝基苯酚，但是贵金属成本较高，经济实用性较低。另外，光催化降解法与纳米贵金属颗粒降解法中的催化剂均 较难回收。 At present, there are mainly two methods for the catalytic degradation of 4-nitrophenol: photocatalytic degradation and nano-precious metal particle catalytic degradation. Photocatalytic degradation is mainly when semiconductors (such as nano TiO 2 , nano ZnO, etc.) are irradiated by ultraviolet light with a wavelength of less than 387.5 nm, the electrons in the valence band are excited, and the transition enters the conduction band, thus generating negative charge on the conduction band electronic high activity (E -), leaving a hole in the valence band of positively charged (h +), under the action of the electric field, electrons and holes are separated and migrate to different parts of the surface of the particle, form an oxidation - reduction In the system, 4-nitrophenol is used as a sacrificial agent to be catalytically reduced. However, the price of semiconductor materials is relatively high, and photocatalysis has strict requirements on conditions, and the reaction is relatively slow, which cannot be industrialized. Noble metal particles have small particle size and relatively high surface atom occupation. They have unique quantum size effects, surface effects, and macroscopic quantum tunneling effects, which give them many unique optical, electrical, and catalytic properties, and have extremely high specific surface area and It is surface active and can efficiently catalyze the degradation of 4-nitrophenol, but the cost of precious metals is higher and the economical and practicality is lower. In addition, the catalysts in the photocatalytic degradation method and the nano-precious metal particle degradation method are more difficult to recover.
发明内容Summary of the invention
本发明要解决的技术问题/达到的目的至少包括：(1)制备绿色可再生的能够处理4-硝基苯酚(如废水中)的催化剂；(2)催化效率高；(3)重复利用时催化效率高；以减少现有方法中降解4-硝基苯酚化学药品使用量大，且处理效果不理想等问题。The technical problems to be solved/objectives achieved by the present invention include at least: (1) Preparation of a green and renewable catalyst capable of treating 4-nitrophenol (such as in wastewater); (2) High catalytic efficiency; (3) Recycling The catalytic efficiency is high; in order to reduce the problem of large usage of the degrading 4-nitrophenol chemicals in the existing method, and the unsatisfactory treatment effect.
为此，本发明提供一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜及其制备方法和应用；本发明以纳米纤维素纤维(CNF)为原料，纳米CuO颗粒原位生长在纳米纤维素纤维上，且纳米纤维素纤维表面偶联接枝有胺基，使其具有催化降解4-硝基苯酚的能力，并与聚乙烯醇混合成膜用于污水处理，并且可回收，可为CNF的产业化应用提供新的方向。To this end, the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol and a preparation method and application thereof; the present invention uses nano cellulose fibers (CNF) as raw materials, and nano CuO particles are grown in situ On the nano-cellulose fiber, and the surface of the nano-cellulose fiber is coupled and grafted with amine groups, so that it has the ability to catalyze the degradation of 4-nitrophenol, and is mixed with polyvinyl alcohol to form a film for sewage treatment, and it can be recycled , Which can provide a new direction for the industrial application of CNF.
为实现上述目的，本发明公开了下述技术方案：In order to achieve the above objectives, the present invention discloses the following technical solutions:
本发明提供一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，包括：纳米纤维素纤维(CNF)和纳米CuO颗粒，所述纳米CuO颗粒原位生长在纳米纤维素纤维上，且所述纳米纤维素纤维表面偶联接枝有胺基；所述胺基为醇胺基。The present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, comprising: nano cellulose fibers (CNF) and nano CuO particles, the nano CuO particles being grown in situ on the nano cellulose fibers , And the surface of the nanocellulose fiber is coupled and grafted with an amine group; the amine group is an alcohol amine group.
优选的，所述CNF和纳米CuO颗粒的质量比为1：1～2。Preferably, the mass ratio of the CNF and the nano CuO particles is 1:1-2.
优选的，所述纳米纤维素纤维中的胺基由乙二醇胺提供。Preferably, the amine group in the nanocellulose fiber is provided by glycol amine.
优选的，所述CNF的长度为500～2000nm，直径为10～50nm。Preferably, the CNF has a length of 500-2000 nm and a diameter of 10-50 nm.
本发明还提供上述改性纳米纤维素纤维膜的制备方法，包括如下步骤：The present invention also provides a method for preparing the above-mentioned modified nano-cellulose fiber membrane, which includes the following steps:
(1)将CNF的悬浮液和过氧化氢-氨水混合液混合搅拌均匀，然后离心，将得到的CNF洗涤至中性，备用；(1) Mix the CNF suspension and the hydrogen peroxide-ammonia mixture evenly, then centrifuge, and wash the CNF to neutral for use;
(2)将步骤(1)处理的CNF、水溶性铜源和碱液混合后，在搅拌条件下进行反应至出现黑色，得到CNF@CuO；(2) After mixing the CNF treated in step (1), the water-soluble copper source, and the lye, the reaction is carried out under stirring conditions until black appears to obtain CNF@CuO;
(3)将所述CNF@CuO重新分散并加入硅烷偶联剂中，在水浴条件下进行反应，所述反应完成后，对反应液进行离心、洗涤和收集沉淀，得到疏水改性的CNF@CuO；(3) The CNF@CuO is redispersed and added to the silane coupling agent, and the reaction is carried out under water bath conditions. After the reaction is completed, the reaction solution is centrifuged, washed and precipitated to obtain hydrophobically modified CNF@ CuO;
(4)将所述疏水改性的CNF@CuO加入乙二醇胺，除去反应体系中氧气，在水浴条件下进行反应，所述反应完成后，对反应液进行离心，洗涤和收集沉淀，得到所述接枝有胺基的改性纳米纤维素纤维悬浮液；(4) Add the hydrophobically modified CNF@CuO to glycol amine to remove oxygen from the reaction system, and perform the reaction under water bath conditions. After the reaction is completed, the reaction solution is centrifuged, washed, and the precipitate is collected to obtain The modified nano cellulose fiber suspension grafted with amine groups;
(5)将所述接枝有胺基的改性纳米纤维素纤维悬浮液与聚乙烯醇混合，流延成膜，得到所述改性纳米纤维素纤维膜。(5) Mixing the modified nano-cellulose fiber suspension grafted with amine groups with polyvinyl alcohol, and casting into a film to obtain the modified nano-cellulose fiber film.
优选的，所述步骤(1)中，采用硫酸法制备CNF的悬浮液，并进行超声处理。Preferably, in the step (1), a suspension of CNF is prepared by a sulfuric acid method, and ultrasonic treatment is performed.
优选地，所述步骤(1)中，CNF的悬浮液、过氧化氢-氨水混合液的添加比例为1～2g：10mL。Preferably, in the step (1), the addition ratio of the CNF suspension and the hydrogen peroxide-ammonia mixed liquid is 1 to 2 g: 10 mL.
优选地，所述步骤(1)中，过氧化氢-氨水混合液中两者质量比为1：1～2。Preferably, in the step (1), the mass ratio of the two in the hydrogen peroxide-ammonia mixture is 1:1-2.
优选地，所述步骤(2)中，水溶性铜源包括硫酸铜、硝酸铜和氯化铜中的任意一种。Preferably, in the step (2), the water-soluble copper source includes any one of copper sulfate, copper nitrate and copper chloride.
优选地，所述步骤(2)中，所述碱液为氢氧化钠水溶液或氨水。Preferably, in the step (2), the lye is an aqueous sodium hydroxide solution or ammonia water.
优选地，所述步骤(2)中，所述搅拌的温度为60～90℃。Preferably, in the step (2), the stirring temperature is 60-90°C.
优选的，所述步骤(3)中，所述水浴的温度为50～85℃。Preferably, in the step (3), the temperature of the water bath is 50-85°C.
优选地，所述步骤(3)中，CNF@CuO和硅烷偶联剂质量比为10～5：1。Preferably, in the step (3), the mass ratio of CNF@CuO and the silane coupling agent is 10-5:1.
优选地，所述步骤(3)中，硅烷偶联剂包括3-氨丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的任意一种。Preferably, in the step (3), the silane coupling agent includes 3-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ-(2,3-cyclic Any one of oxypropoxy)propyltrimethoxysilane.
优选地，所述步骤(4)中，除去反应体系中氧气的方法为向反应体系中持续通入氮气。Preferably, in the step (4), the method for removing oxygen in the reaction system is to continuously pass nitrogen into the reaction system.
优选地，所述步骤(4)中，乙二醇胺的用量为1～30wt％。Preferably, in the step (4), the amount of glycol amine is 1-30 wt%.
优选地，所述步骤(4)中，乙二醇胺的用量为5～20wt％。Preferably, in the step (4), the amount of glycol amine is 5-20 wt%.
优选地，所述步骤(4)中，所述水浴的温度为45～60℃。Preferably, in the step (4), the temperature of the water bath is 45-60°C.
优选地，所述步骤(5)中，接枝有胺基的改性纳米纤维素纤维悬浮液与聚乙烯醇的体积比为2～4：1。Preferably, in the step (5), the volume ratio of the modified nanocellulose fiber suspension grafted with amine groups to the polyvinyl alcohol is 2 to 4:1.
优选的，所述步骤(5)中，接枝有胺基的改性纳米纤维素纤维悬浮 液的浓度为1.0wt％、1.2wt％或1.5wt％。Preferably, in the step (5), the concentration of the modified nanocellulose fiber suspension grafted with amine groups is 1.0 wt%, 1.2 wt% or 1.5 wt%.
本发明还提供了一种催化降解4-硝基苯酚的方法：将所述改性纳米纤维素纤维膜加入4-硝基苯酚溶液中，同时加入NaBH 4进行搅拌，催化降解所述4-硝基苯酚。 The present invention also provides a method for catalytic degradation of 4-nitrophenol: adding the modified nano cellulose fiber membrane to the 4-nitrophenol solution, and at the same time adding NaBH 4 for stirring, to catalytically degrade the 4-nitrophenol.基phenol.
优选地，所述改性纳米纤维素纤维膜与NaBH 4的质量比为1～10：6。 Preferably, the mass ratio of the modified nanocellulose fiber membrane to NaBH 4 is 1-10:6.
优选的，所述催化降解完成后，通过离心分离，回收所述改性纳米纤维素纤维膜。Preferably, after the catalytic degradation is completed, the modified nanocellulose fiber membrane is recovered by centrifugal separation.
优选地，所述回收后得到的改性纳米纤维素膜用于催化降解4-硝基苯酚。Preferably, the modified nano cellulose membrane obtained after the recovery is used to catalyze the degradation of 4-nitrophenol.
本发明还提供了所述的改性纳米纤维素纤维在环境、化工和医药领域中的应用。The invention also provides the application of the modified nano cellulose fiber in the fields of environment, chemical industry and medicine.
与现有技术相比，本发明取得了以下有益效果：Compared with the prior art, the present invention has achieved the following beneficial effects:
(1)本发明以CNF为原料，改性是在水系条件下进行，使其具有绿色环保、可再生的优点。(1) The present invention uses CNF as a raw material, and the modification is carried out under water system conditions, so that it has the advantages of green, environmental protection and renewable.
(2)本发明的改性CNF膜对可降解4-硝基苯酚具有优异的催化降解能力，首次使用时降解率可达94％以上，并且可以在短时间内高效的催化降解4-硝基苯酚，高效的催化降解能力使得本发明的改性CNF膜用量相对传统的化学药品处理4-硝基苯酚而言，能够显著降低用量。(2) The modified CNF membrane of the present invention has excellent catalytic degradation ability for degradable 4-nitrophenol, the degradation rate can reach more than 94% when used for the first time, and it can efficiently catalyze and degrade 4-nitrophenol in a short time. With respect to phenol, the high-efficiency catalytic degradation ability of the present invention enables the modified CNF membrane of the present invention to significantly reduce the dosage compared with the traditional chemical treatment of 4-nitrophenol.
(3)本发明的改性CNF膜能够将4-硝基苯酚转化成4-氨基苯酚，不仅可以降低4-硝基苯酚的毒性，而且4-氨基苯酚可以作为精细有机化工中间体被利用。(3) The modified CNF membrane of the present invention can convert 4-nitrophenol into 4-aminophenol, not only can reduce the toxicity of 4-nitrophenol, but also 4-aminophenol can be used as a fine organic chemical intermediate.
(4)本发明的改性CNF膜可通过去离子水洗涤回收，是一种清洁产品；而且经过多次使用-回收-使用后，对4-硝基苯酚的降解率依然保持在85％以上。(4) The modified CNF membrane of the present invention can be recovered by washing with deionized water, which is a clean product; and after multiple use-recovery-use, the degradation rate of 4-nitrophenol still remains above 85% .
(5)本发明制备方法简单、降解能力强、实用性强，易于推广。(5) The preparation method of the present invention is simple, has strong degradation ability, strong practicability, and is easy to popularize.
具体实施方式Detailed ways
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be pointed out that the following detailed descriptions are all illustrative and are intended to provide further descriptions of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如，在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terms used here are only for describing specific embodiments, and are not intended to limit the exemplary embodiments according to the present invention. For example, as used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should also be understood that when the terms "comprising" and/or "including" are used in this specification, they Indicates that there are features, steps, operations, devices, components, and/or combinations thereof.
正如前文所述，结合绿色可再生材料处理废水中的4-硝基苯酚，减少化学药品的使用，提高处理效率等是实现4-硝基苯酚降解的重要途径。因此，本发明提出了一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜及其制备方法。As mentioned above, the treatment of 4-nitrophenol in wastewater with green renewable materials, reducing the use of chemicals, and improving treatment efficiency are important ways to achieve 4-nitrophenol degradation. Therefore, the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol and a preparation method thereof.
本发明提供了能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，包括：纳米纤维素纤维和纳米CuO颗粒，所述纳米CuO颗粒原位生长在所述纳米纤维素纤维上，且所述纳米纤维素纤维表面偶联接枝有胺基。The present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, comprising: nano cellulose fibers and nano CuO particles, the nano CuO particles are grown in situ on the nano cellulose fibers, and The surface of the nano cellulose fiber is coupled and grafted with an amine group.
在一些典型实施方式中，所述改性纳米纤维素纤维膜中CNF长度为500～2000nm，直径为10～50nm；In some typical embodiments, the CNF in the modified nanocellulose fiber membrane has a length of 500-2000 nm and a diameter of 10-50 nm;
在一些典型实施方式中，所述改性纳米纤维素纤维膜中CNF和所述纳米CuO颗粒的质量比为1：1～2，过量的纳米CuO颗粒会导致CNF网络结构中分散的纳米CuO颗粒增加，并损失在洗涤过程中。In some typical embodiments, the mass ratio of CNF and nano CuO particles in the modified nanocellulose fiber membrane is 1:1 to 2, and an excessive amount of nano CuO particles will cause nano CuO particles dispersed in the CNF network structure Increase and loss in the washing process.
在一些典型实施方式中，所述改性纳米纤维素纤维膜中的胺基由乙二醇胺提供。In some typical embodiments, the amine group in the modified nanocellulose fiber membrane is provided by glycol amine.
本发明还提供了所述的改性纳米纤维素纤维膜的制备方法，其特征在于，包括如下步骤：The present invention also provides a method for preparing the modified nanocellulose fiber membrane, which is characterized in that it comprises the following steps:
(1)将CNF的悬浮液和过氧化氢-氨水混合液混合搅拌均匀，然后离心，将得到的CNF洗涤至中性，备用；(1) Mix the CNF suspension and the hydrogen peroxide-ammonia mixture evenly, then centrifuge, and wash the CNF to neutral for use;
(2)将步骤(1)处理的纳米纤维素纤维、水溶性铜源和碱液混合后，在搅拌条件下进行反应至出现黑色，得到CNF@CuO；(2) After mixing the nanocellulose fibers treated in step (1), the water-soluble copper source and the lye, the reaction is carried out under stirring conditions until black appears, and CNF@CuO is obtained;
(3)将所述CNF@CuO重新分散并加入硅烷偶联剂中，在水浴条件下进行反应，所述反应完成后，对反应液进行离心、洗涤和收集沉淀，得到疏水改性的CNF@CuO；(3) The CNF@CuO is redispersed and added to the silane coupling agent, and the reaction is carried out under water bath conditions. After the reaction is completed, the reaction solution is centrifuged, washed and precipitated to obtain hydrophobically modified CNF@ CuO;
(4)将所述疏水改性的CNF@CuO中加入乙二醇胺，除去反应体系 中氧气，在水浴条件下进行反应，所述反应完成后，对反应液进行离心，洗涤和收集沉淀，得到接枝有胺基的改性纳米纤维素纤维悬浮液；(4) Add glycol amine to the hydrophobically modified CNF@CuO to remove oxygen from the reaction system, and perform the reaction under water bath conditions. After the reaction is completed, the reaction solution is centrifuged, washed, and the precipitate is collected. Obtain a modified nano cellulose fiber suspension grafted with amine groups;
(5)将所述接枝有胺基的改性纳米纤维素纤维悬浮液与聚乙烯醇混合，流延成膜，得到所述改性纳米纤维素纤维膜。(5) Mixing the modified nano-cellulose fiber suspension grafted with amine groups with polyvinyl alcohol, and casting into a film to obtain the modified nano-cellulose fiber film.
在一些典型实施方式中，所述步骤(1)中，采用硫酸法制备CNF的悬浮液，并进行超声处理。In some typical embodiments, in the step (1), a suspension of CNF is prepared by a sulfuric acid method, and ultrasonic treatment is performed.
在一些典型实施方式中，所述步骤(1)中，CNF的悬浮液和过氧化氢-氨水混合液的添加比例为1～2g：10mL。In some typical embodiments, in the step (1), the addition ratio of the CNF suspension and the hydrogen peroxide-ammonia mixed liquid is 1 to 2 g: 10 mL.
在一些典型实施方式中，所述步骤(1)中，过氧化氢氨水混合液中两者质量比为1：1～2。加入过氧化氢-氨水混合液的主要目的是脱除CNF表面附着的磺酸基团，增大羟基含量，从而提高CNF的表面活性，有利于后续改性过程。In some typical embodiments, in the step (1), the mass ratio of the two in the hydrogen peroxide ammonia water mixture is 1:1-2. The main purpose of adding the hydrogen peroxide-ammonia mixture is to remove the sulfonic acid groups attached to the surface of the CNF and increase the hydroxyl content, thereby increasing the surface activity of the CNF, which is beneficial to the subsequent modification process.
在一些典型实施方式中，所述步骤(2)中，水溶性铜源包括硫酸铜、硝酸铜或氯化铜。In some typical embodiments, in the step (2), the water-soluble copper source includes copper sulfate, copper nitrate or copper chloride.
在一些典型实施方式中，所述步骤(2)中，所述碱液为氢氧化钠水溶液或氨水。In some typical embodiments, in the step (2), the lye is an aqueous sodium hydroxide solution or ammonia water.
在一些典型实施方式中，所述步骤(2)中，所述搅拌的温度为60～90℃。In some typical embodiments, in the step (2), the stirring temperature is 60-90°C.
在一些典型实施方式中，所述步骤(3)中，所述水浴的温度为50～85℃。In some typical embodiments, in the step (3), the temperature of the water bath is 50-85°C.
在一些典型实施方式中，所述步骤(3)中，CNF@CuO和硅烷偶联剂的质量比为10～5：1。硅烷偶联剂主要接枝在CNF表面用于提高其疏水性，且硅烷偶联剂可偶联接枝乙二醇胺，但CNF@CuO和硅烷偶联剂的质量比超过5：1会导致CNF疏水性明显增大，不利于改性CNF膜在水中的催化降解作用。In some typical embodiments, in the step (3), the mass ratio of CNF@CuO and the silane coupling agent is 10-5:1. The silane coupling agent is mainly grafted on the surface of CNF to improve its hydrophobicity, and the silane coupling agent can be coupled and grafted with glycol amine, but the mass ratio of CNF@CuO and silane coupling agent exceeding 5:1 will cause The hydrophobicity of CNF is obviously increased, which is not conducive to the catalytic degradation of modified CNF membrane in water.
在一些典型实施方式中，所述步骤(3)中，硅烷偶联剂包括3-氨丙基三乙氧基硅烷，γ-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的任意一种。In some typical embodiments, in the step (3), the silane coupling agent includes 3-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ-(2 Any one of ,3-glycidoxy)propyltrimethoxysilane.
在一些典型实施方式中，所述步骤(4)中，除去反应体系中氧气的方法为向反应体系中持续通入氮气。In some typical embodiments, in the step (4), the method for removing oxygen in the reaction system is to continuously pass nitrogen into the reaction system.
在一些典型实施方式中，所述步骤(4)中，所述乙二醇胺的用量为1～30wt％。加入乙二醇胺的主要目的是接枝具有催化活性的醇胺基团，取代硅烷基团上的-Cl。In some typical embodiments, in the step (4), the amount of the glycol amine is 1-30 wt%. The main purpose of adding glycol amine is to graft the catalytically active alcohol amine group to replace -Cl on the silane group.
在一些典型实施方式中，所述步骤(4)中，所述乙二醇胺的用量为5～20wt％。本发明进一步研究发现，当乙二醇胺用量小于5wt％时，改性CNF膜对4-硝基苯酚的催化降解效果不佳；当乙二醇胺用量大于20wt％，继续增大乙二醇胺用量对4-硝基苯酚的催化降解效果影响不大。In some typical embodiments, in the step (4), the amount of the glycol amine is 5-20 wt%. Further research of the present invention found that when the amount of glycolamine is less than 5wt%, the modified CNF membrane has a poor catalytic degradation effect on 4-nitrophenol; when the amount of glycolamine is greater than 20wt%, continue to increase the amount of glycol amine The amount of amine has little effect on the catalytic degradation of 4-nitrophenol.
在一些典型实施方式中，所述步骤(4)中，所述水浴的温度为45～60℃。In some typical embodiments, in the step (4), the temperature of the water bath is 45-60°C.
在一些典型实施方式中，所述步骤(5)中，接枝有胺基的改性纳米纤维素纤维悬浮液与聚乙烯醇的体积比为2～4：1。In some typical embodiments, in the step (5), the volume ratio of the modified nanocellulose fiber suspension grafted with amine groups to the polyvinyl alcohol is 2 to 4:1.
在一些典型实施方式中，所述步骤(5)中，接枝有胺基的改性纳米纤维素纤维悬浮液的浓度为1.0wt％、1.2wt％或1.5wt％。In some typical embodiments, in the step (5), the concentration of the modified nanocellulose fiber suspension grafted with amine groups is 1.0 wt%, 1.2 wt%, or 1.5 wt%.
本发明还提供了一种催化降解4-硝基苯酚的方法：将所述改性纳米纤维素纤维膜加入4-硝基苯酚溶液中，同时加入NaBH 4进行搅拌，催化降解所述4-硝基苯酚。 The present invention also provides a method for catalytic degradation of 4-nitrophenol: adding the modified nano cellulose fiber membrane to the 4-nitrophenol solution, and at the same time adding NaBH 4 for stirring, to catalytically degrade the 4-nitrophenol.基phenol.
在一些典型实施方式中，所述催化降解4-硝基苯酚的方法中改性CNF膜与NaBH 4的质量比为1～10：6，超过10：6对4-硝基苯酚的去除率提高不明显。 In some typical embodiments, the mass ratio of the modified CNF membrane to NaBH 4 in the method for catalytic degradation of 4-nitrophenol is 1-10:6, and the removal rate of 4-nitrophenol is improved by more than 10:6. Not obvious.
在一些典型实施方式中，所述催化降解完成后，通过离心分离，回收所述改性纳米纤维素膜；或通过去离子水洗涤即可回收改性CNF膜，并重新用于4-硝基苯酚的催化降解。In some typical embodiments, after the catalytic degradation is completed, the modified nanocellulose membrane can be recovered by centrifugal separation; or the modified CNF membrane can be recovered by washing with deionized water and reused for 4-nitro Catalytic degradation of phenol.
本发明还提供了所述改性纳米纤维素纤维在环境、化工和医药领域中的应用。The invention also provides the application of the modified nano cellulose fiber in the fields of environment, chemical industry and medicine.
现结合具体实施方式对本发明进一步进行说明。The present invention will now be further described in conjunction with specific embodiments.
实施例1Example 1
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步 骤如下：1. A modified nano-cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF悬浮液的制备：(1) Preparation of CNF suspension:
a)将桉木浆板置于去离子水中浸泡至完全疏解，打浆至打浆度为48°SR，脱水处理并密封平衡12h后测定水分备用。a) Soak the eucalyptus pulp board in deionized water until it is completely decomposed, beat the pulp to a beating degree of 48°SR, dehydrate and seal and balance for 12 hours, and then measure the water content for later use.
b)取适量浆料(相比于绝干浆)置于三口烧瓶中，以酸浆比18：1加入适量64％的浓硫酸，于50℃水浴中酸水解反应1h，反应完成后加入去离子水终止反应，离心洗涤至上清液pH为3，沉淀置换透析至透析液呈中性。b) Take an appropriate amount of slurry (compared to the absolute dry slurry) and place it in a three-necked flask, add an appropriate amount of 64% concentrated sulfuric acid with a physique ratio of 18:1, and react with acid hydrolysis in a water bath at 50°C for 1 hour. After the reaction is complete, add it to the flask. Ionized water terminated the reaction, centrifuged and washed until the pH of the supernatant was 3, and precipitated replacement dialysis until the dialysate was neutral.
c)取出沉淀，置于超声波细胞粉碎机中以1200W功率处理30min，再经高压匀质机一级阀压强80bar，二级阀压强350bar均质15min，得到CNF悬浮液。c) Take out the precipitate, place it in an ultrasonic cell pulverizer and treat it with a power of 1200W for 30 minutes, and then homogenize it for 15 minutes with a first-stage valve pressure of 80 bar and a second-stage valve pressure of 350 bar in a high pressure homogenizer to obtain a CNF suspension.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取10g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：1)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF于三口烧瓶中，将0.2M的CuSO 4与1.0M的NaOH分散在100mL去离子水中并转移至三口烧瓶中，60℃下搅拌4h至溶液呈黑色，得到CNF@CuO，其中CNF与CuO的质量比为1：1。 e) Take 8g of CNF treated in step d) in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask, stir at 60°C for 4h until the solution turns black. Get CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入0.8g 3-氨丙基三乙氧基硅烷，于50℃水浴中搅拌6h，离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 0.8g of 3-aminopropyltriethoxysilane, in a 50℃ water bath Stir in medium for 6 hours, centrifuge and wash until the filtrate does not contain chloride ions, collect the precipitate and measure the moisture. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取6g步骤f)的CNF@CuO-APTS于三口烧瓶中，加入1wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，45℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take 6g of CNF@CuO-APTS of step f) in a three-necked flask, add 1wt% glycol amine (relative to CNF@CuO-APTS of step f)), and continue to pour in nitrogen, and react in a 45℃ water bath 12h, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain the modified CNF suspension;
h)将步骤g)的改性CNF的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积4：1混合，流延成膜，即得。h) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1mmol/L的4-硝基苯酚50mL置于烧杯中，加入100mg改性CNF膜，同时加入600mg NaBH 4，机械搅拌5min，离心回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例2Example 2
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取10g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：1)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF于三口烧瓶中，将0.2M的CuSO 4与1.0M的NaOH分散在100mL去离子水中并转移至三口烧瓶中，60℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO，其中CNF与CuO的质量比为1：1。 e) Take 8g of CNF treated in step d) in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask, stir at 60°C for 4h until the solution turns black. The obtained precipitate is CNF@CuO, and the mass ratio of CNF to CuO is 1:1.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入0.8gγ-甲基丙烯酰氧基丙基三甲氧基硅烷，于50℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 0.8g of γ-methacryloxypropyltrimethoxysilane to Stir in a water bath at 50°C for 6 hours, wash with ethanol by centrifugation until the filtrate does not contain chloride ions, collect the precipitate and measure the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g步骤f)的CNF@CuO-MPS于三口烧瓶中，加入5wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，45℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take the above 6g of CNF@CuO-MPS from step f) in a three-necked flask, add 5wt% glycolamine (relative to CNF@CuO-APTS in step f)), and continue to pour nitrogen into a water bath at 45°C React for 12 hours, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain a modified CNF suspension;
h)将步骤g)的改性CNF的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积4：1混合，流延成膜，即得。h) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1mmol/L的4-硝基苯酚50mL置于烧杯中，加入100mg改性CNF膜，同时加入600mg NaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and apply it to UV-visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例3Example 3
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取10g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：1)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的纳米纤维素纤置于三口烧瓶中，将0.2M的CuSO 4与1.0M的NaOH分散在100mL去离子水中并转移至三口烧瓶中，60℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO，其中CNF与CuO的质量比为1：1。 e) Take 8g of the nanocellulose fiber treated in step d) and place it in a three-necked flask. Disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 60°C for 4h. The solution is black, and the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入0.8gγ-甲基丙烯酰氧基丙基三甲氧基硅烷，于50℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 0.8g of γ-methacryloxypropyltrimethoxysilane to Stir in a water bath at 50°C for 6 hours, wash with ethanol by centrifugation until the filtrate does not contain chloride ions, collect the precipitate and measure the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g上述的CNF@CuO-MPS于三口烧瓶中，加入5wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，45℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take the above 6g of the above CNF@CuO-MPS in a three-necked flask, add 5wt% glycol amine (relative to the CNF@CuO-APTS in step f)), and continue to blow in nitrogen, and react in a 45℃ water bath for 12h , Centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain the modified CNF suspension;
h)将步骤g)的改性CNF的悬浮液(浓度为1.2wt％)与聚乙烯醇按照体积4：1混合，流延成膜，即得。h) The modified CNF suspension (concentration of 1.2 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1mmol/L的4-硝基苯酚50mL置于烧杯中，加入100mg改性CNF膜，同时加入600mg NaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and apply it to UV-visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例4Example 4
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取20g上述纳米纤维素纤丝的悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：2)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 20g of the suspension of the above nanocellulose filaments into a three-necked flask, add 100mL of H 2 O 2 and NH 3 ·H 2 O mixture (mass ratio 1:2), mechanically stir at room temperature for 1 hour, and deionize The water is centrifuged and washed to neutrality, the precipitate is collected and the water content is measured.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的CuCl 2与1.0M的NaOH分散在100mL去离子水中并转移至三口烧瓶中，70℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO,其中CNF与CuO的质量比为1：2。 e) Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.0gγ-(2,3-环氧丙烷)丙基三甲氧基硅烷，于60℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.0g of γ-(2,3-propylene oxide) propyltrimethoxy Silane was stirred in a water bath at 60°C for 6 hours, washed with water and ethanol by centrifugation until the filtrate did not contain chloride ions, and the precipitate was collected and the water content was measured. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g上述的CNF@CuO-EPPM置于三口烧瓶中，加入10wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，50℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take the above 6g of the above CNF@CuO-EPPM and place it in a three-necked flask, add 10wt% glycol amine (relative to the CNF@CuO-APTS in step f)), and continue to pour in nitrogen, and react in a water bath at 50°C 12h, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain the modified CNF suspension;
h)将所述改性CNF膜的悬浮液(浓度为1.5wt％)与聚乙烯醇按照体积3：1混合，流延成膜，即得。h) Mix the suspension of the modified CNF membrane (with a concentration of 1.5 wt%) and polyvinyl alcohol in a volume of 3:1, and cast into a film to obtain.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1mmol/L的4-硝基苯酚50mL置于烧杯中，加入100mg改性CNF膜，同时加入200mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1mmol/L 4-nitrophenol into a beaker, add 100mg of modified CNF membrane, and at the same time add 200mg of NaBH 4 , mechanically stir for 5 minutes, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例5Example 5
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取20g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：2)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 20g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 2) at room temperature with mechanical stirring IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的CuCl 2与1.0M的NaOH分散在100mL去离子水中并转移至三口烧瓶中，70℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO,其中CNF与CuO的质量比为1：2。 e) Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.0g 3-氨丙基三乙氧基硅烷，于60℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.0g of 3-aminopropyltriethoxysilane, in a 60℃ water bath After stirring for 6 hours, centrifuge with water and ethanol to wash until the filtrate does not contain chloride ions, collect the precipitate and measure the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g步骤f)的CNF@CuO-APTS置于三口烧瓶中，加入10wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，50℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take the above 6g of CNF@CuO-APTS from step f) and place it in a three-necked flask, add 10wt% glycol amine (relative to CNF@CuO-APTS in step f)), and continue to pour in nitrogen gas in a water bath at 50°C React for 12 hours, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain a modified CNF suspension;
h)将步骤g)的改性CNF的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积3：1混合，流延成膜，即得。h) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol in a volume of 3:1, and cast into a film to obtain.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1mmol/L的4-硝基苯酚50mL置于烧杯中，加入200mg改性CNF 膜，同时加入200mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 200mg of NaBH 4 at the same time, mechanically stir for 5 min, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy in UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例6Example 6
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取20g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：2)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 20g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 2) at room temperature with mechanical stirring IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的CuCl 2与1.0M的NaOH分散在100mL去离子水中并转移至三口烧瓶中，70℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO,其中CNF与CuO的质量比为1：2。 e) Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.0gγ-甲基丙烯酰氧基丙基三甲氧基硅烷，于60℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.0g of γ-methacryloxypropyltrimethoxysilane to Stir in a water bath at 60°C for 6 hours, wash with ethanol by centrifugation until the filtrate does not contain chloride ions, collect the precipitate and measure the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g上述的CNF@CuO-MPS于三颈烧瓶中，加入10wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，50℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take 6g of the above-mentioned CNF@CuO-MPS in a three-necked flask, add 10wt% glycol amine (relative to the CNF@CuO-APTS in step f)), and continue to blow in nitrogen, and react in a water bath at 50°C. 12h, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain the modified CNF suspension;
h)将步骤g)的改性CNF的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积3：1混合，流延成膜，即得。h) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol in a volume of 3:1, and cast into a film to obtain.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1mmol/L的4-硝基苯酚50mL置于烧杯中，加入300mg改性CNF 膜，同时加入200mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 300mg of modified CNF membrane, and add 200mg of NaBH 4 at the same time, mechanically stir for 5min, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy in UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例7Example 7
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取10g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：1)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的Cu(NO 3) 2与1.0M的NaOH分散在100mL去离子水中并转移至三口烧瓶中，80℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO,其中CNF与CuO的质量比为1：1。 e) Take 8g of CNF processed in step d) and place it in a three-necked flask. Disperse 0.2M Cu(NO 3 ) 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 80°C for 4h Until the solution turns black, the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.3g 3-氨丙基三乙氧基硅烷，于70℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.3g of 3-aminopropyltriethoxysilane, in a 70℃ water bath After stirring for 6 hours, centrifuge and wash with water and ethanol until the filtrate does not contain chloride ions, collect the precipitate and measure the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g步骤f)的CNF@CuO-APTS于三颈烧瓶中，加入15wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，55℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take the above 6g of CNF@CuO-APTS from step f) in a three-necked flask, add 15wt% glycol amine (relative to CNF@CuO-APTS in step f)), and continue to pour in nitrogen, 55℃ water bath React for 12 hours, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain a modified CNF suspension;
h)将步骤g)的改性CNF的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积2：1混合，流延成膜，即得。h) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 2:1, and cast into a film to obtain it.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1mmol/L的4-硝基苯酚50mL置于烧杯中，加入400mg改性CNF膜，同时加入100mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜， 并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 400mg of modified CNF membrane and 100mg of NaBH 4 at the same time, mechanically stir for 5 min, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例8Example 8
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取10g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：1)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的Cu(NO 3) 2与1.0M的NH 3·H 2O分散在100mL去离子水中并转移至三口烧瓶中，80℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO,其中CNF与CuO的质量比为1：1。 e) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M Cu(NO 3 ) 2 and 1.0M NH 3 ·H 2 O in 100 mL deionized water and transfer to the three-necked flask, Stir at 80°C for 4h until the solution turns black. The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.3gγ-甲基丙烯酰氧基丙基三甲氧基硅烷，于70℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.3g of γ-methacryloxypropyltrimethoxysilane to Stir in a water bath at 70°C for 6 hours, wash with ethanol by centrifugation until the filtrate does not contain chloride ions, collect the precipitate and measure the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g上述的CNF@CuO-MPS于三颈烧瓶中，加入15wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，55℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液；g) Take the above 6g of the above CNF@CuO-MPS in a three-necked flask, add 15wt% glycol amine (relative to the CNF@CuO-APTS in step f)), and continue to pour in nitrogen, and react in a 55℃ water bath 12h, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain the modified CNF suspension;
h)将步骤g)的改性CNF的悬浮液(浓度为1.5wt％)与聚乙烯醇按照体积2：1混合，流延成膜，即得。h) The modified CNF suspension (concentration of 1.5 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 2:1, and cast into a film to obtain.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取1.5mmol/L的4-硝基苯酚50mL置于烧杯中，加入200mg改性CNF膜，同时加入100mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜， 并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Take 50mL of 1.5mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 100mg of NaBH 4 at the same time, mechanically stir for 5min, centrifuge and wash to recover the modified CNF membrane, and collect the upper layer liquid and apply it to ultraviolet visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例9Example 9
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取10g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mLH 2O 2与NH 3·H 2O混合液(质量比为1：1)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 · H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的Cu(NO 3) 2与1.0M的NH 3·H 2O分散在100mL去离子水中并转移至三口烧瓶中，80℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO,其中CNF与CuO的质量比为1：1。 e) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M Cu(NO 3 ) 2 and 1.0M NH 3 ·H 2 O in 100 mL deionized water and transfer to the three-necked flask, Stir at 80°C for 4h until the solution turns black. The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.3g 3-氨丙基三乙氧基硅烷，于70℃水浴中搅拌6h，水乙醇离心法洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.3g of 3-aminopropyltriethoxysilane, in a 70℃ water bath After stirring for 6h, washing with water-ethanol centrifugation until the filtrate does not contain chloride ions, collect the precipitate and measure the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g上述的CNF@CuO-APTS于三颈烧瓶中，加入15wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，55℃水浴中反应12h，离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液膜；g) Take 6g of the above-mentioned CNF@CuO-APTS in a three-necked flask, add 15wt% glycol amine (relative to the CNF@CuO-APTS in step f)), and continue to pour in nitrogen, and react in a 55℃ water bath 12h, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain a modified CNF suspension membrane;
h)将所述改性CNF膜的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积2：1混合，流延成膜，即得。h) Mix the suspension of the modified CNF membrane (with a concentration of 1.0% by weight) and polyvinyl alcohol in a volume of 2:1, and cast into a film to obtain.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取2mmol/L的4-硝基苯酚50mL置于烧杯中，加入200mg改性CNF膜，同时加入100mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm 波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Put 50mL of 2mmol/L 4-nitrophenol in a beaker, add 200mg of modified CNF membrane and 100mg of NaBH 4 at the same time, mechanically stir for 5min, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy in UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例10Example 10
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取20g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mL H 2O 2与NH 3·H 2O混合液(质量比为1：2)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 20g of the CNF suspension of step c) and place it in a three-necked flask, add 100 mL of a mixture of H 2 O 2 and NH 3 ·H 2 O (mass ratio 1:2), mechanically stir for 1 hour at room temperature, deionized water Centrifuge and wash until neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的CuSO 4与1.0M的NH 3·H 2O分散在100mL去离子水中并转移至三口烧瓶中，90℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO，其中CNF与CuO的质量比为1：2。 e) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NH 3 ·H 2 O in 100mL deionized water and transfer to the three-necked flask, stir at 90 ℃ 4h until the solution turns black, the precipitate obtained is CNF@CuO, and the mass ratio of CNF to CuO is 1:2.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.6gγ-甲基丙烯酰氧基丙基三甲氧基硅烷，于85℃水浴中搅拌6h，离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.6g of γ-methacryloxypropyltrimethoxysilane, Stir in a water bath at 85°C for 6 hours, centrifuge and wash until the filtrate does not contain chloride ions, collect the precipitate and measure the moisture. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g上述的CNF@CuO-MPS于三颈烧瓶中，加入20wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，60℃水浴中反应12h，水乙醇离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液膜；g) Take 6g of the above-mentioned CNF@CuO-MPS in a three-necked flask, add 20wt% glycol amine (relative to the CNF@CuO-APTS in step f)), and continue to bubbling in nitrogen, and react in a 60℃ water bath 12h, centrifugal washing with water and ethanol until the filtrate does not contain chloride ions, and collect the precipitate to obtain a modified CNF suspension membrane;
h)将所述改性CNF膜的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积2：1混合，流延成膜，即得。h) Mix the suspension of the modified CNF membrane (with a concentration of 1.0% by weight) and polyvinyl alcohol in a volume of 2:1, and cast into a film to obtain.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取2.5mmol/L的4-硝基苯酚50mL置于烧杯中，加入200mg改性CNF膜，同时加入60mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行 回用。 Take 50mL of 2.5mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 60mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper layer liquid and apply it to ultraviolet visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
实施例11Example 11
1、一种能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，具体步骤如下：1. A modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, the specific steps are as follows:
(1)CNF的制备：同实施例1。(1) Preparation of CNF: Same as Example 1.
(2)改性CNF膜的制备：(2) Preparation of modified CNF membrane:
d)取20g步骤c)的CNF悬浮液置于三口烧瓶中，加入100mL H 2O 2与NH 3·H 2O混合液(质量比为1：2)，室温下机械搅拌1h，去离子水离心洗涤至中性，收集沉淀并测量水分。 d) Take 20g of the CNF suspension of step c) and place it in a three-necked flask, add 100 mL of a mixture of H 2 O 2 and NH 3 ·H 2 O (mass ratio 1:2), mechanically stir for 1 hour at room temperature, deionized water Centrifuge and wash until neutral, collect the precipitate and measure the moisture.
e)取8g经过步骤d)处理的CNF置于三口烧瓶中，将0.2M的CuSO 4与1.0M的NH 3·H 2O散在100mL去离子水中并转移至三口烧瓶中，90℃下搅拌4h至溶液呈黑色，得到的沉淀即为CNF@CuO，其中CNF与CuO的质量比为1：2。 e) Take 8g of CNF treated in step d) and place it in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NH 3 ·H 2 O in 100 mL of deionized water and transfer to the three-necked flask, stir at 90°C for 4h Until the solution turns black, the precipitate obtained is CNF@CuO, and the mass ratio of CNF to CuO is 1:2.
f)取8g步骤e)的CNF@CuO，加入160mL水乙醇(水和乙醇的质量比为1：3)重新分散，并加入1.6gγ-(2,3-环氧丙氧)丙基三甲氧基硅烷，于85℃水浴中搅拌6h，水乙醇离心洗涤至滤液中不含氯离子，收集沉淀并测量水分。得到的沉淀即为疏水改性的CNF@CuO(CNF@CuO-APTS)。f) Take 8g of CNF@CuO from step e), add 160mL of water ethanol (the mass ratio of water to ethanol is 1:3) to redisperse, and add 1.6g of γ-(2,3-glycidoxy)propyltrimethoxy Silane, stirred in a water bath at 85°C for 6 hours, washed with water and ethanol by centrifugation until the filtrate does not contain chloride ions, collected the precipitate and measured the water content. The resulting precipitate is the hydrophobically modified CNF@CuO (CNF@CuO-APTS).
g)取上述6g上述的CNF@CuO-EPPM于三颈烧瓶中，加入30wt％乙二醇胺(相对于步骤f)的CNF@CuO-APTS)，并持续通入氮气，60℃水浴中反应12h，水乙醇离心洗涤至滤液不含氯离子，收集沉淀，即得改性CNF悬浮液膜；g) Take the above 6g of the above CNF@CuO-EPPM in a three-necked flask, add 30wt% glycol amine (relative to the CNF@CuO-APTS in step f)), and continue to blow in nitrogen, and react in a 60℃ water bath 12h, centrifugal washing with water and ethanol until the filtrate does not contain chloride ions, and collect the precipitate to obtain a modified CNF suspension membrane;
h)将所述改性CNF膜的悬浮液(浓度为1.0wt％)与聚乙烯醇按照体积2：1混合，流延成膜，即得。h) Mix the suspension of the modified CNF membrane (with a concentration of 1.0% by weight) and polyvinyl alcohol in a volume of 2:1, and cast into a film to obtain.
2、改性CNF膜催化降解4-硝基苯酚测试：2. Test of catalytic degradation of 4-nitrophenol by modified CNF membrane:
取3mmol/L的4-硝基苯酚50mL置于烧杯中，加入200mg改性CNF膜，同时加入60mgNaBH 4，机械搅拌5min，离心洗涤回收改性CNF膜，并将上层液体收集并于紫外可见光分光光度计下进行扫描，记录在400nm波长出的吸收率，计算出其浓度。去离子水洗涤回收改性CNF膜并进行回用。 Place 50mL of 3mmol/L 4-nitrophenol in a beaker, add 200mg of modified CNF membrane and 60mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
性能测试：Performance Testing:
以滤液中的4-硝基苯酚的浓度为性能测试指标，测定实施例1～11制备的改性纳米纤维素纤丝处理4-硝基苯酚后的滤液浓度。测试方法为：分别配置0.005g/L、0.001g/L、0.0015g/L、0.002g/L、0.0025g/L的4-硝基苯酚标样，置于紫外可见光分光光度计中测定吸光度，并确定标准曲线，如表1所示。Taking the concentration of 4-nitrophenol in the filtrate as a performance test index, the concentration of the filtrate after the 4-nitrophenol was treated with the modified nanocellulose filaments prepared in Examples 1-11 was measured. The test method is: configure the 4-nitrophenol standard samples of 0.005g/L, 0.001g/L, 0.0015g/L, 0.002g/L, 0.0025g/L, and place them in an ultraviolet-visible spectrophotometer to measure the absorbance. And determine the standard curve, as shown in Table 1.
分别将滤液置于紫外可见光分光光度计中测定吸光度，并根据标准曲线计算其浓度，测试结果如表2和3所示。The filtrate was placed in an ultraviolet-visible spectrophotometer to measure the absorbance, and the concentration was calculated according to the standard curve. The test results are shown in Tables 2 and 3.
表1 4-硝基苯酚标样紫外可见光吸光度Table 1 UV-Vis absorbance of 4-nitrophenol standard sample
4-硝基苯酚浓度/g/LConcentration of 4-nitrophenol/g/L 0.00050.0005 0.0010.001 0.00150.0015 0.0020.002 0.00250.0025
吸光度/T％Absorbance/T% 0.022860.02286 0.035590.03559 0.040330.04033 0.048750.04875 0.057150.05715
根据计算，可知标准曲线为y＝16.827x+0.0151；其中，x为4-硝基苯酚浓度，g/L；y为紫外可见光吸光度，T％。According to the calculation, it can be seen that the standard curve is y=16.827x+0.0151; where x is the concentration of 4-nitrophenol, g/L; and y is the absorbance of ultraviolet-visible light, T%.
表2实施例1～5制备的改性纳米纤维素纤丝对4-硝基苯酚后的去除率Table 2 The removal rate of 4-nitrophenol by the modified nanocellulose filaments prepared in Examples 1 to 5
实施例序号Example number 11 22 33 44 55
吸光度/T％Absorbance/T% 0.146320.14632 0.129310.12931 0.072690.07269 0.061530.06153 0.054250.05425
浓度/mmol/LConcentration/mmol/L 0.056510.05651 0.048830.04883 0.024620.02462 0.019850.01985 0.016740.01674
去除率/％Removal rate/% 94.3594.35 95.1295.12 97.5497.54 98.0298.02 98.3398.33
回用次数Reuse times 2525 2525 2525 2525 2525
回用之后去除率/％Removal rate after reuse/% 85.0885.08 85.4685.46 86.1286.12 88.1588.15 88.6788.67
表3实施例6～11制备的改性纳米纤维素纤丝对4-硝基苯酚后的去除率Table 3 The removal rate of 4-nitrophenol by the modified nanocellulose filaments prepared in Examples 6-11
实施例序号Example number 66 77 88 99 1010 1111
吸光度/T％Absorbance/T% 0.032600.03260 0.016110.01611 0.067800.06780 0.110580.11058 0.259290.25929 0.363350.36335
浓度/mmol/LConcentration/mmol/L 0.007480.00748 0.004430.00443 0.022530.02253 0.040820.04082 0.104400.10440 0.148890.14889
去除率/％Removal rate/% 99.2699.26 99.5699.56 98.5098.50 97.9697.96 95.8395.83 95.0495.04
回用次数Reuse times 2525 2525 2525 2525 2525 2525
回用之后去除率/％Removal rate after reuse/% 89.8889.88 90.1290.12 89.7589.75 89.5389.53 89.4289.42 89.1389.13
从表2和表3可以看出，采用本发明的方法对CNF进行改性之后，可以在短时间内高效的催化降解4-硝基苯酚，去离子多次洗涤回收后仍 然具有优异的4-硝基苯酚去除能力。From Table 2 and Table 3, it can be seen that after the CNF is modified by the method of the present invention, 4-nitrophenol can be catalyzed and degraded efficiently in a short time, and it still has excellent 4-nitrophenol after repeated washing and recovery. Nitrophenol removal ability.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The description of the above embodiments is only used to help understand the method and core idea of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (25)

  1. 能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜，其特征在于，包括：纳米纤维素纤维和纳米CuO颗粒，所述纳米CuO颗粒原位生长在所述纳米纤维素纤维上，且所述纳米纤维素纤维表面偶联接枝有胺基；所述胺基为醇胺基。The modified nano-cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol is characterized by comprising: nano-cellulose fibers and nano-CuO particles, and the nano-CuO particles are grown in situ on the nano-cellulose fibers, and The surface of the nano cellulose fiber is coupled and grafted with an amine group; the amine group is an alcohol amine group.
  2. 如权利要求1所述的改性纳米纤维素纤维膜，其特征在于，所述纳米纤维素纤维和所述纳米CuO颗粒的质量比为1：1～2。The modified nanocellulose fiber membrane of claim 1, wherein the mass ratio of the nanocellulose fibers and the nano CuO particles is 1:1-2.
  3. 如权利要求1所述的改性纳米纤维素纤维膜，其特征在于，所述纳米纤维素纤维中的胺基由乙二醇胺提供。The modified nanocellulose fiber membrane of claim 1, wherein the amine group in the nanocellulose fiber is provided by glycol amine.
  4. 如权利要求1～3任一项所述的改性纳米纤维素纤维膜，其特征在于，所述纳米纤维素纤维的长度为500～2000nm，直径为10～50nm。The modified nanocellulose fiber membrane according to any one of claims 1 to 3, wherein the nanocellulose fiber has a length of 500-2000 nm and a diameter of 10-50 nm.
  5. 能够催化降解4-硝基苯酚的改性纳米纤维素纤维膜的制备方法，其特征在于，包括如下步骤：The preparation method of modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol is characterized in that it comprises the following steps:
    (1)将CNF的悬浮液和过氧化氢-氨水混合液混合搅拌均匀，然后离心，将得到的CNF洗涤至中性，备用；(1) Mix the CNF suspension and the hydrogen peroxide-ammonia mixture evenly, then centrifuge, and wash the CNF to neutral for use;
    (2)将步骤(1)处理的纳米纤维素纤维、水溶性铜源和碱液混合后，在搅拌条件下进行反应至出现黑色，得到CNF@CuO；(2) After mixing the nanocellulose fibers treated in step (1), the water-soluble copper source and the lye, the reaction is carried out under stirring conditions until black appears, and CNF@CuO is obtained;
    (3)将所述CNF@CuO重新分散并加入硅烷偶联剂中，在水浴条件下进行反应，所述反应完成后，对反应液进行离心、洗涤收集沉淀，得到疏水改性的CNF@CuO；(3) Redisperse the CNF@CuO and add it to the silane coupling agent, and react in a water bath. After the reaction is completed, the reaction solution is centrifuged and washed to collect the precipitate to obtain the hydrophobically modified CNF@CuO ；
    (4)将所述疏水改性的CNF@CuO中加入乙二醇胺，除去反应体系中氧气，在水浴条件下进行反应，所述反应完成后，反应液进行离心，洗涤收集沉淀，得到接枝有胺基的改性纳米纤维素纤维悬浮液；(4) Add glycol amine to the hydrophobically modified CNF@CuO to remove oxygen from the reaction system, and perform the reaction under water bath conditions. After the reaction is completed, the reaction solution is centrifuged, washed to collect the precipitate, and obtained Modified nano cellulose fiber suspension with amine groups;
    (5)将所述接枝有胺基的改性纳米纤维素纤维悬浮液与聚乙烯醇混合，流延成膜，得到所述改性纳米纤维素纤维膜。(5) Mixing the modified nano-cellulose fiber suspension grafted with amine groups with polyvinyl alcohol, and casting into a film to obtain the modified nano-cellulose fiber film.
  6. 如权利要求5所述的制备方法，其特征在于，所述步骤(1)中，采用硫酸法制备CNF的悬浮液，并进行超声处理。The preparation method according to claim 5, characterized in that, in the step (1), a suspension of CNF is prepared by a sulfuric acid method, and ultrasonic treatment is performed.
  7. 如权利要求5所述的制备方法，其特征在于，所述步骤(1)中， CNF的悬浮液和过氧化氢-氨水混合液的添加比例为1～2g：10mL。The preparation method according to claim 5, characterized in that, in the step (1), the addition ratio of the CNF suspension and the hydrogen peroxide-ammonia mixed liquid is 1 to 2 g: 10 mL.
  8. 如权利要求5所述的制备方法，其特征在于，所述步骤(1)中，过氧化氢-氨水混合液中两者质量比为1：1～2。The preparation method according to claim 5, characterized in that, in the step (1), the mass ratio of the two in the hydrogen peroxide-ammonia mixture is 1:1-2.
  9. 如权利要求5所述的制备方法，其特征在于，所述步骤(2)中，水溶性铜源包括硫酸铜、硝酸铜和氯化铜中的任意一种。The preparation method according to claim 5, wherein in the step (2), the water-soluble copper source includes any one of copper sulfate, copper nitrate and copper chloride.
  10. 如权利要求5所述的制备方法，其特征在于，所述步骤(2)中，碱液为氢氧化钠水溶液或氨水。The preparation method according to claim 5, wherein in the step (2), the lye is aqueous sodium hydroxide or ammonia water.
  11. 如权利要求5所述的制备方法，其特征在于，所述步骤(2)中，搅拌的温度为60～90℃。The preparation method according to claim 5, characterized in that, in the step (2), the stirring temperature is 60-90°C.
  12. 如权利要求5所述的制备方法，其特征在于，所述步骤(3)中，水浴的温度为50～85℃。The preparation method according to claim 5, wherein in the step (3), the temperature of the water bath is 50-85°C.
  13. 如权利要求5所述的制备方法，其特征在于，所述步骤(3)中，CNF@CuO和硅烷偶联剂质量比为10～5：1。The preparation method according to claim 5, characterized in that, in the step (3), the mass ratio of CNF@CuO and the silane coupling agent is 10-5:1.
  14. 如权利要求5所述的制备方法，其特征在于，所述步骤(3)中，硅烷偶联剂包括3-氨丙基三乙氧基硅烷，γ-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的任意一种。The preparation method according to claim 5, characterized in that, in the step (3), the silane coupling agent comprises 3-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane Either of oxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane.
  15. 如权利要求5所述的制备方法，其特征在于，所述步骤(4)中，除去反应体系中氧气的方法为向反应体系中持续通入氮气。The preparation method according to claim 5, characterized in that, in the step (4), the method for removing oxygen in the reaction system is to continuously pass nitrogen into the reaction system.
  16. 如权利要求5所述的制备方法，其特征在于，所述步骤(4)中，所述乙二醇胺的用量为1～30wt％。The preparation method according to claim 5, characterized in that, in the step (4), the amount of the glycol amine is 1-30 wt%.
  17. 如权利要求16所述的制备方法，其特征在于，所述步骤(4)中，所述乙二醇胺的用量为5～20wt％。The preparation method according to claim 16, characterized in that, in the step (4), the amount of the glycol amine is 5-20 wt%.
  18. 如权利要求5所述的制备方法，其特征在于，所述步骤(4)中，水浴的温度为45～60℃。The preparation method according to claim 5, characterized in that, in the step (4), the temperature of the water bath is 45-60°C.
  19. 如权利要求5所述的制备方法，其特征在于，所述步骤(5)中，接枝有胺基的改性纳米纤维素纤维悬浮液与聚乙烯醇的体积比为2～4：1。The preparation method according to claim 5, characterized in that, in the step (5), the volume ratio of the modified nanocellulose fiber suspension grafted with amine groups to the polyvinyl alcohol is 2 to 4:1.
  20. 如权利要求19所述的制备方法，其特征在于，所述步骤(5)中，接枝有胺基的改性纳米纤维素纤维悬浮液的浓度为1.0wt％、1.2wt％或1.5wt％。The preparation method according to claim 19, wherein, in the step (5), the concentration of the modified nanocellulose fiber suspension grafted with amine groups is 1.0wt%, 1.2wt% or 1.5wt% .
  21. 一种催化降解4-硝基苯酚的方法：将权利要求1～4任一项所述的改性纳米纤维素纤维膜或由权利要求5～20任一项所述的方法制备得到的改性纳米纤维素纤维膜加入4-硝基苯酚溶液中，同时加入NaBH 4进行搅拌，催化降解所述4-硝基苯酚。 A method for catalytic degradation of 4-nitrophenol: the modified nanocellulose fiber membrane according to any one of claims 1 to 4 or the modified nanocellulose fiber membrane prepared by the method according to any one of claims 5 to 20 The nano cellulose fiber membrane is added to the 4-nitrophenol solution, and NaBH 4 is added for stirring at the same time, to catalytically degrade the 4-nitrophenol.
  22. 如权利要求21所述的方法，其特征在于，所述改性纳米纤维素纤维膜与NaBH 4的质量比为1～10：6。 The method of claim 21, wherein the mass ratio of the modified nanocellulose fiber membrane to NaBH 4 is 1-10:6.
  23. 如权利要求21所述的方法，其特征在于，所述催化降解完成后，通过离心分离，回收所述改性纳米纤维素膜。22. The method of claim 21, wherein after the catalytic degradation is completed, the modified nanocellulose membrane is recovered by centrifugal separation.
  24. 如权利要求23所述的方法，其特征在于，所述回收后得到的改性纳米纤维素膜用于催化降解4-硝基苯酚。The method according to claim 23, wherein the modified nanocellulose membrane obtained after the recovery is used for catalytic degradation of 4-nitrophenol.
  25. 权利要求1～4任一项所述的改性纳米纤维素纤维膜和/或权利要求5～20任一项所述的方法制备的改性纳米纤维素纤维膜在环境、化工和医药领域中的应用。The modified nanocellulose fiber membrane according to any one of claims 1 to 4 and/or the modified nanocellulose fiber membrane prepared by the method according to any one of claims 5 to 20 are used in the fields of environment, chemical industry and medicine Applications.
PCT/CN2020/076726 2019-10-09 2020-02-26 Modified cnf membrane capable of catalytically degrading 4-nitrophenol, preparation method therefor and application thereof WO2021068449A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021517357A JP7132663B2 (en) 2019-10-09 2020-02-26 Modified CNF Membrane Capable of Catalytic Decomposition of 4-Nitrophenol, Its Preparation Method and Application

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910954943.0A CN110681415B (en) 2019-10-09 2019-10-09 Modified CNF membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof
CN201910954943.0 2019-10-09

Publications (1)

Publication Number Publication Date
WO2021068449A1 true WO2021068449A1 (en) 2021-04-15

Family

ID=69111829

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/076726 WO2021068449A1 (en) 2019-10-09 2020-02-26 Modified cnf membrane capable of catalytically degrading 4-nitrophenol, preparation method therefor and application thereof

Country Status (3)

Country Link
JP (1) JP7132663B2 (en)
CN (1) CN110681415B (en)
WO (1) WO2021068449A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115055208A (en) * 2022-06-24 2022-09-16 安庆市长三角未来产业研究院 Preparation method of two-phase flow catalytic membrane, two-phase flow catalytic membrane and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110681415B (en) * 2019-10-09 2021-10-15 齐鲁工业大学 Modified CNF membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof
CN111974359B (en) * 2020-09-01 2022-10-25 齐鲁工业大学 Preparation and application of nano-cellulose/layered double-metal hydroxide composite material with adsorptivity and in-situ catalysis performance
CN112156810B (en) * 2020-09-17 2023-04-07 齐鲁工业大学 Nano cellulose membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104492486A (en) * 2014-12-22 2015-04-08 中国科学院化学研究所 Biomass load type nano-metal catalyst and preparation method and application thereof
CN106512876A (en) * 2016-11-17 2017-03-22 陕西盛迈石油有限公司 Preparation method of carbonized bacterial cellulose wrapped copper
CN110227509A (en) * 2019-06-24 2019-09-13 中北大学 A kind of carbon dots/copper oxide/mesoporous hydroxyapatite catalysis material preparation method of efficient reduction p-nitrophenol
CN110681415A (en) * 2019-10-09 2020-01-14 齐鲁工业大学 Modified CNF membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101418063B (en) * 2008-12-08 2010-12-22 中国热带农业科学院农产品加工研究所 Method for preparing natural rubber-silicon dioxide nano composite material by in-situ grafting polymerization
CN103642062B (en) * 2013-12-05 2016-04-27 江南大学 A kind of preparation method of high catalytic activity Red copper oxide/regenerated cellulose laminated film
CA2979303A1 (en) * 2014-03-11 2015-09-17 Les Innovations Materium Inc. Processes for preparing silica-carbon allotrope composite materials and using same
AU2014404426B2 (en) * 2014-08-25 2017-11-02 Halliburton Energy Services, Inc. Crush-resistant proppant particulates for use in subterranean formation operations
CN107185591B (en) * 2017-05-16 2019-09-06 郑州轻工业学院 A kind of preparation method and applications for the cellulose paper base nano silver catalysis material that can be recycled
CN107213916B (en) * 2017-06-27 2019-10-01 广西大学 The preparation method and applications of modified wood fibre element ester group class fenton catalyst
CN108940268B (en) * 2018-07-27 2021-06-01 信阳师范学院 graphene/Pt nano composite aerogel material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104492486A (en) * 2014-12-22 2015-04-08 中国科学院化学研究所 Biomass load type nano-metal catalyst and preparation method and application thereof
CN106512876A (en) * 2016-11-17 2017-03-22 陕西盛迈石油有限公司 Preparation method of carbonized bacterial cellulose wrapped copper
CN110227509A (en) * 2019-06-24 2019-09-13 中北大学 A kind of carbon dots/copper oxide/mesoporous hydroxyapatite catalysis material preparation method of efficient reduction p-nitrophenol
CN110681415A (en) * 2019-10-09 2020-01-14 齐鲁工业大学 Modified CNF membrane capable of catalytically degrading 4-nitrophenol and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BENDI RAMARAJU, IMAE TOYOKO: "Renewable catalyst with Cu nanoparticles embedded into cellulose nano-fiber film", RSC ADVANCES, vol. 3, no. 37, 1 January 2013 (2013-01-01), pages 16279, XP055800768, DOI: 10.1039/c3ra42689k *
JIANG HONG, SUN XIAOXU, DU YAN, CHEN RIZHI, XING WEIHONG: "Catalytic activity of palladium nanoparticles immobilized on an amino-functionalized ceramic membrane support", CHINESE JOURNAL OF CATALYSIS / DALIAN INSTITUTE OF CHEMICAL PHYSICS, ELSEVIER, AMSTERDAM, NL, vol. 35, no. 12, 1 December 2014 (2014-12-01), AMSTERDAM, NL, pages 1990 - 1996, XP055800767, ISSN: 1872-2067, DOI: 10.1016/S1872-2067(14)60190-X *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115055208A (en) * 2022-06-24 2022-09-16 安庆市长三角未来产业研究院 Preparation method of two-phase flow catalytic membrane, two-phase flow catalytic membrane and application thereof

Also Published As

Publication number Publication date
CN110681415B (en) 2021-10-15
JP7132663B2 (en) 2022-09-07
JP2022512559A (en) 2022-02-07
CN110681415A (en) 2020-01-14

Similar Documents

Publication Publication Date Title
WO2021068449A1 (en) Modified cnf membrane capable of catalytically degrading 4-nitrophenol, preparation method therefor and application thereof
Adnan et al. Mitigation of pollutants by chitosan/metallic oxide photocatalyst: a review
Emam et al. Observable removal of pharmaceutical residues by highly porous photoactive cellulose acetate@ MIL-MOF film
Zhou et al. Carbon nitride nanotubes with in situ grafted hydroxyl groups for highly efficient spontaneous H2O2 production
Chen et al. Strategic combination of nitrogen-doped carbon quantum dots and g-C3N4: efficient photocatalytic peroxydisulfate for the degradation of tetracycline hydrochloride and mechanism insight
Vincent et al. Chitosan-supported palladium catalyst. 1. Synthesis procedure
Liu et al. High-efficient catalytic reduction of 4-nitrophenol based on reusable Ag nanoparticles/graphene-loading loofah sponge hybrid
Wang et al. Construction of β-FeOOH@ tunicate cellulose nanocomposite hydrogels and their highly efficient photocatalytic properties
Duan et al. Fabrication of carboxymethylated cellulose fibers supporting Ag NPs@ MOF‐199s nanocatalysts for catalytic reduction of 4‐nitrophenol
Peng et al. A new strategy to construct cellulose-chitosan films supporting Ag/Ag2O/ZnO heterostructures for high photocatalytic and antibacterial performance
Hou et al. Efficient degradation of perfluorooctanoic acid by electrospun lignin-based bimetallic MOFs nanofibers composite membranes with peroxymonosulfate under solar light irradiation
Yang et al. Carbon doped Fe3O4 peroxidase-like nanozyme for mitigating the membrane fouling by NOM at neutral pH
CN108246334B (en) Functionalized ternary composite photocatalytic material and preparation method and application thereof
EP2921456A2 (en) Material used in the removal of contaminants from liquid matrices
CN110240723B (en) Ultraviolet high-shielding cellulose membrane and preparation method and application thereof
Faraji et al. Enhanced photocatalytic activity by synergic action of ZIF-8 and NiFe2O4 under visible light irradiation
CN104399535A (en) Preparation method and application thereof of magnetic complex-based catalyst
CN113731395A (en) Zinc stannate photocatalyst rich in oxygen vacancies, preparation method and application
Wang et al. Enhanced performance of β-cyclodextrin modified Cu2O nanocomposite for efficient removal of tetracycline and dyes: Synergistic role of adsorption and photocatalysis
Wang et al. Stable construction of layered reduced grapheme oxide/copper sulfide composites on cellulose fibers with hyperbranched polyamide-amine for efficient photocatalytic degradation of organic dyes
Xue et al. Preparation of g-C3N4 (Ag)/Gr/TiO2 Z-scheme photocatalyst with enhanced reduction property and the efficient degradation of rhodamine B
CN112973744B (en) Photoelectric catalyst and preparation method thereof
CN103331174A (en) Palladium-loaded cadmium sulfide visible-light-induced photocatalyst and preparation method thereof
CN113198515B (en) Ternary photocatalyst and preparation method and application thereof
CN112827366B (en) Preparation and application of nano zero-valent copper-based modified carbon nanotube filter membrane

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021517357

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20874702

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20874702

Country of ref document: EP

Kind code of ref document: A1