CN106732815A - A kind of fiber/CNT/TiO2 three-dimensional recyclable efficient catalytic material and its preparation and application - Google Patents

A kind of fiber/CNT/TiO2 three-dimensional recyclable efficient catalytic material and its preparation and application Download PDF

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CN106732815A
CN106732815A CN201611095891.9A CN201611095891A CN106732815A CN 106732815 A CN106732815 A CN 106732815A CN 201611095891 A CN201611095891 A CN 201611095891A CN 106732815 A CN106732815 A CN 106732815A
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cnt
tio
fiber
water
product
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刘保江
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Donghua University
National Dong Hwa University
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Donghua University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The present invention relates to a kind of fiber/CNT/TiO2Three-dimensional recyclable efficient catalytic material and its preparation and application, multifunctional carbon nanotube are loaded with nano-TiO in textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface2；Prepare：By fiber impregnation to containing CNT composite Ti O2In polyethylene glycol 2000 dispersion liquid, 60 80 DEG C of 2 4h of reaction, drying, washing, repeated impregnations, drying and water-washing process 35 times are obtained final product.Of the invention with low cost, preparation method is simple, and the requirement to equipment is low, and operability is good；Water treatment agent of the invention can go remove water middle and high concentration organic pollution, it is adaptable to the advanced treating of various waste water, environmentally friendly non-secondary pollution, and have the advantages that antibacterial, it is deodorant, other heavy metal ion can be adsorbed.

Description

A kind of fiber/CNT/TiO2Three-dimensional recyclable efficient catalytic material and its preparation And application
Technical field
The invention belongs to catalyst material and its preparation and application field, more particularly to a kind of fiber/CNT/TiO2 Three-dimensional recyclable efficient catalytic material and its preparation and application.
Background technology
The water in the whole world only about 10% is directly used by the mankind.Lion's share, 70% is used for agricultural, and remaining 20% is It is industrial.The blowdown of China is about the 20% of the whole world, and it has to the fresh water of global 5%.Therefore, pollution problem is solved Put on the agenda.In textile printing and dyeing, leather, paper industry process, pollution environment has largely been used and to human body Harmful auxiliary agent, these auxiliary agents pollute environment with the form discharge of liquid mostly, and biological degradability is poor, and toxicity is big, first of dissociating Aldehyde is high, the content overproof of heavy metal ion.Wherein, printing and dyeing dressing is even more and turns into water pollution rich and influential family undisputedly.From Starching start to desizing, wash, scouring and bleaching, mercerising, then dyeing and printing, may also need coating, all related to per procedure by this flow And washing, and need 20L water consumptions per every kilogram of material of procedure.Result is that the water consumption of every kilogram of raw cotton during dressing has added Carry out up to 200L.When showing in shopper window after an in men's style shirt customization for standard, it is being produced and processed more than 2000L water When by (cloth of having used up：Pure cotton, 125g/m).
The method of the treatment waste water for using at present mainly has：Physical partition method, biological degradation method, chemical decomposition method, but this A little methods all have some limitations, and are unfavorable for sustainable development.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of fiber/CNT/TiO2Three-dimensional is recyclable efficiently to urge Change material and its preparation and application, the inventive method is simple to operate, and with low cost, the requirement to equipment is low；Water treatment agent is applicable In the advanced treating of various waste water, environmentally friendly non-secondary pollution.
A kind of fiber/CNT/TiO of the invention2The recyclable efficient catalytic material of three-dimensional, multifunctional carbon nanotube exists Textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface is loaded with nano-TiO2, form fiber/carbon and receive Mitron/TiO2The recyclable catalysis material of three-dimensional.
The specific surface area of the multifunctional nano pipe is 20~150m2/g；The nano-TiO2Grain size for 15~ 200nm；Textile fabric is flexible textile fiber；Nano-TiO2It is 1 with the mass ratio of multifunctional nano pipe:5~20.
A kind of fiber/CNT/TiO of the invention2The preparation method of the recyclable efficient catalytic material of three-dimensional, including：
(1) by TiO2, stabilizer, template, multifunctional carbon nanotube be added in phosphate buffer, stirring 30~ 60min, forms suspension, then alkali lye regulation pH=5~6,180 DEG C of 3~5h of reaction, obtains multifunctional carbon nanotube and is combined TiO2；Wherein, TiO2It is 1 with the mass ratio of multifunctional carbon nanotube:5~1:20；
(2) fiber impregnation is to containing 0.05~0.75g/L CNT composite Tis O2With the poly- second two of 0.025~0.375g/L In the dispersion liquid of alcohol 2000,60-80 DEG C of reaction 2-4h, drying, washing, repeated impregnations, drying and water-washing process 3-5 times obtain final product fibre Dimension/CNT/TiO2The recyclable efficient catalytic material of three-dimensional.
TiO in the step (1)2Concentration be 0.01~0.2mol/L；Stabilizer is disodium ethylene diamine tetraacetate, second two One kind in the sodium of amine tetraacethyl four, sodium gluconate, BTCA, stabilizer concentration is 0.01~0.1mol/L.
Template is mass ratio 1 in the step (1)：3 triblock polyether P123's and triblock copolymer F127 is mixed Compound；Template agent concentration is 0.01~0.1mol/L.
In the step (1) phosphate buffer by 0.025~0.05mol/L of concentration sodium dihydrogen phosphates and 0.05~ 0.1mol/L dibastic sodium phosphates are constituted；Alkali lye is：The NaOH of 0.5mol/L~1.5mol/L or the aqueous solution of potassium hydroxide.
The step：
A CNT CNTs is added to FeCl by ()2In solution, pH=3 is adjusted, be subsequently adding H2O2, room temperature ultrasound 0.5- 2h, room temperature magnetic agitation 6-8h, suction filtration washing to neutrality, suction filtration, vacuum drying obtain product a；Wherein CNT CNTs, FeCl2Solution, H2O2Ratio be 150~200mg：30~40mL：30~40mL；It is preferred that CNT CNTs, FeCl2Solution, H2O2Ratio be 200mg：40mL：40mL；Wherein it is vacuum dried to be vacuum dried 24h at 60 DEG C；
B () in there-necked flask is dried, product a is scattered in solvent DMF under logical condition of nitrogen gas, ice-water bath cooling, 0 DEG C of addition NaH, stirs 20-30min, is then gradually warmed up to 85-90 DEG C, is added dropwise over 1- perfluoro-hexyl iodides, ultrasonic reaction 18-24h, add water quenching reaction, washing, in vacuum drying oven 50 DEG C dry 96h, obtain black particle product b；Wherein product a, Solvent, the ratio of NaH, 1- perfluoro-hexyl iodide are 1.5~3g：100~200mL：300~522mg：2-3mL；
Preferred product a, solvent, the ratio of NaH, 1- perfluoro-hexyl iodide are 3g：200mL：522mg：3mL；
C be dispersed in water for product b by (), add NaOH, 0.5~1h of ultrasonic disperse, Cyanuric Chloride to add after being dispersed in water Enter in reaction system, 0~5 DEG C of stirring reaction 24-48h, centrifuge washing (successively with water and ethanol centrifuge washing), 25 DEG C of vacuum are dried Dry 96h, obtains product c；Wherein product b, NaOH, the ratio of Cyanuric Chloride are 1~2g：300~438mg：1~2g；It is preferred that producing Thing b, NaOH, the ratio of Cyanuric Chloride are 2g：438mg：2g；
Under (d) logical condition of nitrogen gas, product c, triethylamine, DMF, ice-water bath cooling, at 0 DEG C are added in there-necked flask is dried It is added dropwise over acryloyl chloride (by volume 1:10 are dissolved in DMF), ultrasonic reaction 12-24h, centrifuge washing (successively with ethanol and Water centrifuge washing), room temperature in vacuo drying obtains black solid product d；Wherein product c, triethylamine, DMF, the ratio of acryloyl chloride Example is 1~1.5g：3~2.4mL：100~150mL：0.5~1mL；It is preferred that：Product c, triethylamine, DMF, the ratio of acryloyl chloride It is 1.5g：2.4mL：150mL：1mL；
(e) product d, dimethylphosphite, DMF mixing, it (is by volume 0.3 that DBU is dissolved in into solvent:20 are dissolved in solvent In DMF) in after be added dropwise in reaction system, 25 DEG C of ultrasonic reaction 24-48h, centrifuge washing (successively with second alcohol and water be centrifuged wash Wash (300mL × 3 time)), room temperature in vacuo drying obtains multifunctional carbon nanotube；Wherein product d, methyl phosphite, the ratio of DBU Example is 1g, 300~415mg：0.5mol；Wherein preferred product d, methyl phosphite, the ratio of DBU are 1g：415mg：0.5mol.
FeCl in the step (a)2The mass percentage concentration of solution is 30%.
Sodium carbonate liquor regulation pH value in the step (a).
A kind of fiber/CNT/TiO of the invention2The application of the recyclable efficient catalytic material of three-dimensional, as water process The application of agent, for the treatment of waste water, specially by fiber/CNT/TiO2The recyclable efficient catalytic material of three-dimensional is added In waste water, daylight illumination 3-8h.
CNT as a kind of porous mass, with special interlayer characteristic, can be in its area load TiO2Particulate, system It is standby into loaded catalyst.This loaded photocatalyst can improve the dispersiveness of photochemical catalyst, beneficial to recycling and reusing. The present invention constructs nano semiconductor material in high specific area carbon pipe surface, then will load the high-specific surface area of semi-conducting material Carbon pipe constructs three-dimensional continuous structure in fabric face, then forms new textile fabric/CNT/heterogeneous semiconductor continuous Network, using the porous and capillary effect of flexible fibrous material, makes fiber to adsorb pollutant, while can lead to again Absorption pollutant is crossed in fiber surface enrichment for nano-photocatalyst material provides high concentration reactant bad border, this is largely On accelerate photocatalytic degradation reaction rate.Additionally, during the suction-operated of fiber is also possible to produce photocatalytic degradation reaction Between accessory substance generation when be adsorbed and be further oxided to be degraded to simple inorganic matter, such as carbon dioxide and water.So Fiber can not only concentration pollutant, accelerate photocatalytic degradation reaction, and intermediate by-products can be reduced, release in time is produced Thing, constantly advances degradation reaction.The effective discrete nucleation material of high-specific surface area of CNT is also given full play to simultaneously, is increased Catalyst and the contact interface of pollutant, for light-catalyzed reaction provides more reactivity points, and guarantee to realize photoproduction The directional transmissions of electronics, itself and hole separative efficiency are effectively improved, improve its photocatalytic activity.
The features such as present invention is using the porous of CNT, high adsorption capacity and easily separated water and TiO2Photocatalysis live Property combines, by nano-TiO2Successfully load on CNT, being prepared into can be suspended in waste water and can be suitable The visible-light photocatalysis material of the high catalytic activity that profit is separated from water, and it is applied to the advanced treating of waste water, Ke Yishi It is a technology for environment-friendly type rather than being transferred to elsewhere now to water middle and high concentration organic pollution oxidation removal.
Beneficial effect
(1) present invention is with low cost, and preparation method is simple, and the requirement to equipment is low, and operability is good；
(2) water treatment agent of the invention can go to remove water middle and high concentration organic pollution, it is adaptable to the depth of various waste water Treatment, environmentally friendly non-secondary pollution, and have the advantages that antibacterial, it is deodorant, other heavy metal ion can be adsorbed；
(3) water treatment agent of the invention can overcome the shortcomings of existing silver orthophosphate composite water disposal agent, and water treatment efficiency is good, Can recycle.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiment 1
(1) 150mg CNTs are added to the mass percentage concentration 30%FeCl of 30mL2In solution, pH=3 is adjusted, then Add 30mL H2O2, room temperature ultrasound 0.5h, room temperature magnetic agitation 6h, add water 500mL, suction filtration washing to neutrality, suction filtration.At 60 DEG C Lower vacuum drying 24h obtains product a；
Under logical condition of nitrogen gas, 1.5g products a is being scattered in 100mL DMF in drying there-necked flask, ice-water bath is cold But, 0 DEG C of addition NaH 300mg, continues to stir 20min.Then 85 DEG C are gradually warmed up to, 2mL 1- perfluoro hexyls are added dropwise over Iodine, ultrasonic reaction 18h, plus a small amount of water quenching is reacted, successively DMF, second alcohol and water centrifuge washing.The black particle product b for obtaining 50 DEG C dry 96h in vacuum drying oven；
1g black products b is dispersed in 50mL water, 300mg NaOH, ultrasonic disperse 0.5h, 1g Cyanuric Chloride point is added It is dispersed in 50mL water, in addition there-necked flask, 0 DEG C of stirring reaction 24h.Water and ethanol centrifuge washing are used successively.25 DEG C of vacuum are dried Dry 96h, obtains product c；Under logical condition of nitrogen gas, 1g product c, triethylamine 2.4mL, DMF are added in there-necked flask is dried 100mL.Ice-water bath is cooled down, and acryloyl chloride 0.5mL (being dissolved in 10mL DMF), ultrasonic reaction 12h are added dropwise at 0 DEG C.Use successively Second alcohol and water centrifuge washing.The black solid product d for obtaining, room temperature in vacuo drying；
1g product d, dimethylphosphite 300mg, DMF 150mL are added in there-necked flask, by 0.3mL DBU (0.5mol) It is dissolved in 20mL DMF, is added dropwise in above-mentioned there-necked flask, 25 DEG C of ultrasonic reaction 24h.Second alcohol and water centrifuge washing is used successively (300mL × 3 time) room temperature in vacuo is dried, and obtains multifunctional carbon nanotube e.
(2) by TiO2, disodium ethylene diamine tetraacetate (stabilizer), mass ratio be 1：3 triblock polyether P123 and three embedding Multifunctional carbon nanotube is added to concentration and is in the mixture (template) and above-mentioned steps (1) of section copolymer F127 In the buffer solution of 0.025mol/L sodium dihydrogen phosphates and 0.05mol/L dibastic sodium phosphates composition, 30min is stirred, form suspension；Its In, TiO2Concentration for 0.01mol/L, stabilizer concentration for 0.01mol/L, template concentration be 0.05mol/L.
(3) pH value for adjusting above-mentioned suspension with the sodium hydrate aqueous solution of concentration 0.5mol/L is 5, at 80 DEG C of heating, Backflow 6h, filtering obtains CNT composite Ti O2Green Water Treatment Reagents；Wherein, TiO2With the mass ratio of multifunctional carbon nanotube It is 1:5.
(4) flaxen fiber is impregnated into and contains 0.05g/L, CNT composite Ti O2With 0.025g/L polyethylene glycol 2000s point In dispersion liquid, 60 DEG C of reaction 2h, drying, washing, repeated impregnations, drying and water-washing process 3 times obtain final product fiber/CNT/TiO2 The recyclable efficient catalytic material of three-dimensional.
Embodiment 2
(1) 175mg CNTs are added to the 30%FeCl of 35mL2In solution, pH=3 is adjusted, be subsequently adding 35mL H2O2, room temperature ultrasound 1.5h, room temperature magnetic agitation 87h, add water 500mL, suction filtration washing to neutrality, suction filtration.The vacuum at 60 DEG C Dry 24h and obtain product a；
Under logical condition of nitrogen gas, 2.5g products a is being scattered in 150mL DMF in drying there-necked flask, ice-water bath is cold But, 0 DEG C of addition NaH 411mg, continues to stir 30min.Then 88 DEG C are gradually warmed up to, 2.5mL 1- perfluoro hexyls are added dropwise over Iodine, ultrasonic reaction perfluoro-hexyl iodide, ultrasonic reaction 20h.Plus a small amount of water quenching reaction, DMF, second alcohol and water centrifuge washing successively. The black particle product b for obtaining dries 96h for 50 DEG C in vacuum drying oven；
1.5g products b is dispersed in 50mL water, 438mg NaOH, the dispersion of ultrasonic disperse 1h, 1.5g Cyanuric Chloride is added In 50mL water, in addition there-necked flask, 2.5 DEG C of stirring reaction 36h.Water and ethanol centrifuge washing are used successively.25 DEG C of vacuum are dried Dry 96h, obtains product c；
Under logical condition of nitrogen gas, 1.5g product c, triethylamine 2.8mL, DMF 125mL are added in there-necked flask is dried.Frozen water Bath cooling, is added dropwise over acryloyl chloride 0.75mL (being dissolved in 10mL DMF), ultrasonic reaction 18h at 0 DEG C.Successively with second alcohol and water from The heart is washed.The black solid product d for obtaining, room temperature in vacuo drying；Product 1g d, dimethylphosphite are added in there-necked flask 350mg, DMF 150mL, 0.18mL DBU (0.3mol) are dissolved in 20mL DMF, are added dropwise in above-mentioned there-necked flask, 25 DEG C ultrasonic reaction 36h.Dried with second alcohol and water centrifuge washing (300mL × 3 time) room temperature in vacuo successively, obtain multifunctional C nanometer Pipe e；
(2) by TiO2, sodium gluconate (stabilizer), mass ratio be 1：3 triblock polyether P123 and triblock copolymer Multifunctional carbon nanotube is added to concentration for 0.03mol/L phosphoric acid in the mixture (template) and above-mentioned steps (1) of thing F127 In the buffer solution of sodium dihydrogen and 0.05mol/L dibastic sodium phosphates composition, 45min is stirred, form suspension；Wherein, TiO2Concentration For 0.01mol/L, stabilizer concentration for 0.03mol/L, template concentration be 0.07mol/L.
(3) pH value for adjusting above-mentioned suspension with the sodium hydrate aqueous solution of concentration 0.5mol/L is 7, at 90 DEG C of heating, Backflow 16h, filtering obtains CNT composite Ti O2Green Water Treatment Reagents；Wherein, TiO2With the quality of multifunctional carbon nanotube Than being 1:15.
(4) polyster fibre is impregnated into and contains 0.375g/L, CNT composite Ti O2With 0.15g/L polyethylene glycol 2000s In dispersion liquid, 70 DEG C of reaction 3h, drying, washing, repeated impregnations, drying and water-washing process 4 times, obtain final product fiber/CNT/ TiO2The recyclable efficient catalytic material of three-dimensional.
Embodiment 3
(1) 200mg CNTs are added to the 30%FeCl of 40mL2In solution, pH=3 is adjusted, be subsequently adding 40mL H2O2, room temperature ultrasound 2h, room temperature magnetic agitation 8h, add water 500mL, suction filtration washing to neutrality, suction filtration.It is vacuum dried at 60 DEG C 24h obtains product a；
Under logical condition of nitrogen gas, 3g products a is being scattered in 200mL DMF in drying there-necked flask, ice-water bath cooling, 0 DEG C of addition NaH 522mg, continues to stir 30min.Then 90 DEG C are gradually warmed up to, 3mL 1- perfluoro-hexyl iodides are added dropwise over, are surpassed Phonoresponse perfluoro-hexyl iodide, ultrasonic reaction 24h.Plus a small amount of water quenching reaction, DMF, second alcohol and water centrifuge washing successively.Obtain Black particle product b dries 96h for 50 DEG C in vacuum drying oven；
2g products b is dispersed in 50mL water, adds 438mg NaOH, ultrasonic disperse 1h, 2g Cyanuric Chloride to be dispersed in In 50mL water, in addition there-necked flask, 0~5 DEG C of stirring reaction 48h.Water and ethanol centrifuge washing are used successively.25 DEG C of vacuum dryings 96h, obtains product c；
Under logical condition of nitrogen gas, 1.5g product c, triethylamine 2.4mL, DMF 150mL are added in there-necked flask is dried.Frozen water Bath cooling, is added dropwise over acryloyl chloride 1mL (being dissolved in 10mL DMF), ultrasonic reaction 24h at 0 DEG C.It is centrifuged with second alcohol and water successively Washing.The black solid product d for obtaining, room temperature in vacuo drying；
Product d1g, dimethylphosphite 415mg, DMF 150mL are added in there-necked flask, by 0.3mL DBU (0.5mol) It is dissolved in 20mL DMF, is added dropwise in above-mentioned there-necked flask, 25 DEG C of ultrasonic reaction 48h.Second alcohol and water centrifuge washing is used successively (300mL × 3 time) room temperature in vacuo is dried, and obtains multifunctional carbon nanotube e；
(2) by TiO2, BTCA (stabilizer), mass ratio be 1：3 triblock polyether P123 and triblock copolymer Multifunctional carbon nanotube is added to concentration for 0.05mol/L phosphoric acid in the mixture (template) and above-mentioned steps (1) of thing F127 In the buffer solution of sodium dihydrogen and 0.1mol/L dibastic sodium phosphates composition, 60min is stirred, form suspension；Wherein, TiO2Concentration 0.15mol/L, the concentration of stabilizer are 0.05mol/L, the concentration of template is 0.1mol/L.
(3) pH value for adjusting above-mentioned suspension with the potassium hydroxide aqueous solution of concentration 1.5mol/L is 9, at 100 DEG C of heating, Backflow 24h, filtering obtains CNT composite Ti O2Green Water Treatment Reagents；Wherein, TiO2With the quality of multifunctional carbon nanotube Than being 1:20.
(4) aramid fiber is impregnated into and contains 0.75g/L, CNT composite Ti O2With 0.375g/L polyethylene glycol 2000s In dispersion liquid, 80 DEG C of reaction 4h, drying, washing, repeated impregnations, drying and water-washing process 5 times, obtain final product fiber/CNT/ TiO2The recyclable efficient catalytic material of three-dimensional.
It is process object with the dyeing waste water of the printing and dyeing mill of same time sampling, in containing dyestuff 0.2g/L waste water respectively The water treatment agent of the gained of embodiment 1~3 of addition, by after 6 hours solar radiations, percent of decolourization of the water treatment agent to dyeing waste water It is as shown in the table：

Claims (10)

1. a kind of fiber/CNT/TiO2The recyclable efficient catalytic material of three-dimensional, it is characterised in that：Multifunctional carbon nanotube exists Textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface is loaded with nano-TiO2, form fiber/carbon and receive Mitron/TiO2The recyclable catalysis material of three-dimensional.
2. a kind of fiber/CNT/TiO according to claim 12The recyclable efficient catalytic material of three-dimensional, its feature exists In：The specific surface area of multifunctional nano pipe is 20~150m2/g；The nano-TiO2Grain size be 15~200nm；Weaving Fiber is flexible textile fiber；Nano-TiO2It is 1 with the mass ratio of multifunctional nano pipe:5~20.
3. a kind of fiber/CNT/TiO as described in claim 1-2 is any2The system of the recyclable efficient catalytic material of three-dimensional Preparation Method, including：
(1) by TiO2, stabilizer, template, multifunctional carbon nanotube be added in phosphate buffer, stir 30~60min, Suspension is formed, then alkali lye regulation pH=5~6,180 DEG C of 3~5h of reaction obtain CNT composite Ti O2；
(2) by fiber impregnation to containing 0.05~0.75g/L, CNT composite Ti O2With 0.025~0.375g/L polyethylene glycol In 2000 dispersion liquids, 60-80 DEG C of reaction 2-4h, drying, washing, repeated impregnations, drying and water-washing process 3-5 times, obtain final product fiber/ CNT/TiO2The recyclable efficient catalytic material of three-dimensional.
4. a kind of fiber/CNT/TiO according to claim 32The preparation side of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：TiO in the step (1)2Concentration be 0.01~0.2mol/L；Stabilizer is ethylenediamine tetra-acetic acid two One kind in sodium, tetrasodium ethylenediamine tetraacetate, sodium gluconate, BTCA, stabilizer concentration is 0.01~0.1mol/L.
5. a kind of fiber/CNT/TiO according to claim 32The preparation side of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：Template is mass ratio 1 in the step (1)：3 triblock polyether P123 and triblock copolymer The mixture of F127；Template agent concentration is 0.01~0.1mol/L.
6. a kind of fiber/CNT/TiO according to claim 32The preparation side of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：Phosphate buffer is by 0.025~0.05mol/L of concentration sodium dihydrogen phosphates and 0.05 in the step (1) ~0.1mol/L dibastic sodium phosphates are constituted；Alkali lye is：The NaOH of 0.5mol/L~1.5mol/L or the aqueous solution of potassium hydroxide.
7. a kind of fiber/CNT/TiO according to claim 32The preparation side of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：The preparation method of multifunctional carbon nanotube in the step (1), including：
A CNT CNTs is added to FeCl by ()2In solution, pH=3 is adjusted, be subsequently adding H2O2, room temperature ultrasound 0.5-2h, Room temperature magnetic agitation 6-8h, suction filtration washing to neutrality, suction filtration, vacuum drying obtains product a；Wherein CNT CNTs, FeCl2 Solution, H2O2Ratio be 150~200mg：30~40mL：30~40mL；
B be scattered in product a in solvent under logical condition of nitrogen gas by (), ice-water bath cooling, 0 DEG C of addition NaH, stirs 20-30min, Then 85~90 DEG C are gradually warmed up to, 1- perfluoro-hexyl iodides are added dropwise over, ultrasonic reaction 18-24h, the quenching that adds water is reacted, washing, Dry, obtain product b；Wherein product a, solvent, the ratio of NaH, 1- perfluoro-hexyl iodide are 1.5~3g：100~200mL：300 ~522mg：2-3mL；
C be dispersed in water for product b by (), add NaOH, 0.5~1h of ultrasonic disperse, Cyanuric Chloride to be added after being dispersed in water anti- Answer in system, 0~5 DEG C of stirring reaction 24-48h, centrifuge washing, vacuum drying obtains product c；Wherein product b, NaOH, trimerization The ratio of chlorine cyanogen is 1~2g：300~438mg：1~2g；
D under () logical condition of nitrogen gas, product c, triethylamine, DMF, ice-water bath cooling is added dropwise over acryloyl chloride at 0 DEG C, ultrasound is anti- 12-24h is answered, centrifuge washing, room temperature in vacuo drying obtains product d；The wherein ratio of product c, triethylamine, DMF, acryloyl chloride It is 1~1.5g：3~2.4mL：100~150mL：0.5~1mL；
E () product d, dimethylphosphite, DMF mixing is added dropwise in reaction system after DBU is dissolved in solvent, 25 DEG C surpass Phonoresponse 24-48h, centrifuge washing, room temperature in vacuo drying obtains multifunctional carbon nanotube；Wherein product d, methyl phosphite, The ratio of DBU is 1g, 300~415mg：0.5mol.
8. a kind of fiber/CNT/TiO according to claim 72The preparation side of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：FeCl in the step (a)2The mass percentage concentration of solution is 30%.
9. a kind of fiber/CNT/TiO according to claim 72The preparation side of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：Sodium carbonate liquor regulation pH value in the step (a).
10. a kind of fiber/CNT/TiO as described in claim 1-2 is any2Three-dimensional is recycled answering for efficient catalytic material With, it is characterised in that：As the application of water treatment agent, for the treatment of waste water, specially by fiber/CNT/TiO2Three The recyclable efficient catalytic material of dimension is added in waste water, daylight illumination 3-8h.
CN201611095891.9A 2016-12-02 2016-12-02 A kind of fiber/CNT/TiO2 three-dimensional recyclable efficient catalytic material and its preparation and application Pending CN106732815A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101554586A (en) * 2009-04-30 2009-10-14 东华大学 Method for preparing controllable photodegraded flexible indoor air purifying material
CN104525173A (en) * 2014-12-25 2015-04-22 东华大学 Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and TiO2
CN106076438A (en) * 2016-06-06 2016-11-09 东华大学 A kind of textile fabric/Graphene/TiO2the preparation method of combinational environment catalysis material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101554586A (en) * 2009-04-30 2009-10-14 东华大学 Method for preparing controllable photodegraded flexible indoor air purifying material
CN104525173A (en) * 2014-12-25 2015-04-22 东华大学 Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and TiO2
CN106076438A (en) * 2016-06-06 2016-11-09 东华大学 A kind of textile fabric/Graphene/TiO2the preparation method of combinational environment catalysis material

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Application publication date: 20170531