CN106732795A - A kind of fiber/CNT/BiFeO3Three-dimensional recyclable efficient catalytic material and its preparation and application - Google Patents

A kind of fiber/CNT/BiFeO3Three-dimensional recyclable efficient catalytic material and its preparation and application Download PDF

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Publication number
CN106732795A
CN106732795A CN201611095875.XA CN201611095875A CN106732795A CN 106732795 A CN106732795 A CN 106732795A CN 201611095875 A CN201611095875 A CN 201611095875A CN 106732795 A CN106732795 A CN 106732795A
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bifeo
cnt
fiber
water
dimensional
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刘保江
张俊
张帅
***
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Suzhou Sibin Nano Technology Co Ltd
Donghua University
National Dong Hwa University
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Suzhou Sibin Nano Technology Co Ltd
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
    • B01J31/28—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
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/02—Odour removal or prevention of malodour
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • 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/BiFeO3Three-dimensional recyclable efficient catalytic material and its preparation and application, multifunctional carbon nanotube are loaded with a nanometer BiFeO in textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface3；Prepare：Fiber impregnation is combined BiFeO to containing CNT3In 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/BiFeO3Three-dimensional recyclable efficient catalytic material and its system Standby and application
Technical field
The invention belongs to catalyst material and its preparation and application field, more particularly to a kind of fiber/CNT/ BiFeO3Three-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/BiFeO3Three-dimensional is recyclable efficient Catalysis material and its preparation and application, the inventive method are simple to operate, with low cost, and the requirement to equipment is low；Water treatment agent is fitted For the advanced treating of various waste water, environmentally friendly non-secondary pollution.
A kind of fiber/CNT/BiFeO of the invention3The recyclable efficient catalytic material of three-dimensional, multifunctional carbon nanotube In textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface is loaded with a nanometer BiFeO3, formation fiber/ CNT/BiFeO3The recyclable catalysis material of three-dimensional.
The specific surface area of multifunctional nano pipe is 20~150m2/g；The nanometer BiFeO3It is monoclinic form structure, crystal grain Size is 15~200nm；Textile fabric is flexible textile fiber；Nanometer BiFeO3It is 1 with the mass ratio of multifunctional nano pipe:5 ~20.
A kind of fiber/CNT/BiFeO of the invention3The preparation method of the recyclable efficient catalytic material of three-dimensional, bag Include：
(1) by BiFeO3, 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 BiFeO3；Wherein BiFeO3It is 1 with the mass ratio of multifunctional carbon nanotube:5~1:20；
(2) fiber impregnation to 0.05~0.75g/L CNTs is combined BiFeO3With 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/BiFeO3The recyclable efficient catalytic material of three-dimensional.
BiFeO3 concentration is 0.01~0.2mol/L in suspension in the step (1)；Stabilizer is ethylenediamine tetra-acetic acid One kind in disodium, tetrasodium ethylenediamine tetraacetate, sodium gluconate, BTCA, stabilizer concentration is 0.01~0.1mol/ L.Template is mass ratio 1 in the step (1)：The mixture of 3 triblock polyether P123 and triblock copolymer F127；Mould Plate 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 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 obtain product a；Wherein CNT CNTs, FeCl2Solution, the ratio of H2O2 are 150~200mg：30~40mL：30~40mL；It is preferred that CNT CNTs, FeCl2Solution, The ratio of H2O2 is 200mg：4 0mL：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- perfluor fluorine 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- perfluor fluorine hexyl iodide are 1.5~3g：100~200mL：300~522mg：2-3mL；Preferred product a, Solvent, the ratio of NaH, 1- perfluor fluorine 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/BiFeO of the invention3The application of the recyclable efficient catalytic material of three-dimensional, at water Reason agent
Using for the treatment of waste water, specially by fiber/CNT/BiFeO3The recyclable efficient catalytic material of three-dimensional Material 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 BiFeO3Particulate, It is prepared into loaded catalyst.This loaded photocatalyst can improve the dispersiveness of photochemical catalyst, and profit is repeated beneficial to reclaiming With.The present invention constructs nano semiconductor material in high specific area carbon pipe surface, then will load the Gao Bibiao of semi-conducting material Area carbon pipe constructs three-dimensional continuous structure in fabric face, then forms new textile fabric/CNT/heterogeneous semiconductor Continuous grids structure, using the porous and capillary effect of flexible fibrous material, makes fiber to adsorb pollutant, while again Can be by adsorbing pollutant in fiber surface enrichment for nano-photocatalyst material provides high concentration reactant bad border, this is very big Photocatalytic degradation reaction rate is accelerated in degree.Additionally, the suction-operated of fiber is also possible to make photocatalytic degradation react generation Intermediate by-products 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, in time release Product, 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 Plus catalyst and the contact interface of pollutant, for light-catalyzed reaction provides more reactivity points, and guarantee to realize light Give birth to the directional transmissions of electronics, effectively improve itself and hole separative efficiency, improve its photocatalytic activity.
The features such as present invention is using the porous of CNT, high adsorption capacity and easily separated water and BiFeO3Photocatalysis Activity combines, by nanometer BiFeO3Successfully load on CNT, being prepared into can be suspended in waste water and can The visible-light photocatalysis material of the high catalytic activity to be smoothly separated from water, and it is applied to the advanced treating of waste water, can It is a technique for environment-friendly type rather than being transferred to elsewhere to realize to water middle and high concentration organic pollution oxidation removal Technology.
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- perfluor fluorine 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) it is 1 by BiFeO3, disodium ethylene diamine tetraacetate, mass ratio：3 triblock polyether P123 and triblock copolymer Multifunctional carbon nanotube e is added to concentration for 0.025mol/L sodium dihydrogen phosphates in the mixture and above-mentioned steps (1) of thing F127 In the buffer solution constituted with 0.05mol/L dibastic sodium phosphates, 30min is stirred, form suspension；The wherein concentration of BiFeO3 is 0.01mol/L, the concentration of stabilizer are 0.01mol/L, the concentration of template is 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 the compound BiFeO of CNT3；Wherein BiFeO3 is 1 with the mass ratio of CNT:5.
(4) flaxen fiber is impregnated into and is combined BiFeO containing 0.05g/L CNTs3With 0.025g/L polyethylene glycol 2000s 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/ BiFeO3The 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, be added dropwise over 2.5mL 1- perfluors fluorine oneself Base iodine, ultrasonic reaction perfluoro-hexyl iodide, ultrasonic reaction 20h.Plus a small amount of water quenching reaction, DMF, second alcohol and water are centrifuged and wash successively Wash.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) it is 1 by BiFeO3, sodium gluconate, mass ratio：3 triblock polyether P123 and triblock copolymer F127 Mixture and above-mentioned steps (1) in multifunctional carbon nanotube e be added to concentration for 0.03mol/L sodium dihydrogen phosphates and In the buffer solution of 0.05mol/L dibastic sodium phosphates composition, 45min is stirred, form suspension；The wherein concentration of BiFeO3 is 0.01mol/L, the concentration of stabilizer are 0.03mol/L, the concentration of template is 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 the compound BiFeO of CNT3；Wherein BiFeO3 is 1 with the mass ratio of CNT:15
(4) polyster fibre is impregnated into and is combined BiFeO containing 0.375g/L CNTs3With 0.15g/L polyethylene glycol In 2000 dispersion liquids, 70 DEG C of reaction 3h, drying, washing, repeated impregnations, drying and water-washing process 4 times obtain final product fiber/carbon nanometer Pipe/BiFeO3The 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- perfluor fluorine hexyl iodides are added dropwise over, Ultrasonic reaction 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 dry 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) it is 1 by BiFeO3, BTCA, mass ratio：3 triblock polyether P123 and triblock copolymer F127 Mixture and above-mentioned steps (1) in multifunctional carbon nanotube e be added to concentration for 0.05mol/L sodium dihydrogen phosphates and In the buffer solution of 0.1mol/L dibastic sodium phosphates composition, 60min is stirred, form suspension；The concentration 0.15mol/ of wherein BiFeO3 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 the compound BiFeO of CNT3；Wherein BiFeO3 is 1 with the mass ratio of CNT:20.
(4) aramid fiber is impregnated into and is combined BiFeO containing 0.75g/L CNTs3With 0.375g/L polyethylene glycol In 2000 dispersion liquids, 80 DEG C of reaction 4h, drying, washing, repeated impregnations, drying and water-washing process 5 times obtain final product fiber/carbon nanometer Pipe/BiFeO3The 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 0.2g/l waste water from dyestuff respectively The water treatment agent of the gained of embodiment 1~3 of concentration 5g/l catalysis fibre materials is added, by after 6 hours solar radiations, water process Agent is as shown in the table to the percent of decolourization of dyeing waste water：

Claims (10)

1. a kind of fiber/CNT/BiFeO3The recyclable efficient catalytic material of three-dimensional, it is characterised in that：Multifunctional carbon nanotube In textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface is loaded with a nanometer BiFeO3, formation fiber/ CNT/BiFeO3The recyclable catalysis material of three-dimensional.
2. a kind of fiber/CNT/BiFeO according to claim 13The recyclable efficient catalytic material of three-dimensional, its feature It is：The specific surface area of multifunctional nano pipe is 20~150m2/g；The nanometer BiFeO3It is monoclinic form structure, grain size It is 15~200nm；Textile fabric is flexible textile fiber；Nanometer BiFeO3It is 1 with the mass ratio of multifunctional nano pipe:5~20.
3. a kind of fiber/CNT/BiFeO as described in claim 1-2 is any3The recyclable efficient catalytic material of three-dimensional Preparation method, including：
(1) by BiFeO3, 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 the compound BiFeO of CNT3； Wherein BiFeO3It is 1 with the mass ratio of multifunctional carbon nanotube:5~1:20；
(2) by fiber impregnation to containing 0.05~0.75g/L, CNT is combined BiFeO3With 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/BiFeO3The recyclable efficient catalytic material of three-dimensional.
4. a kind of fiber/CNT/BiFeO according to claim 33The preparation of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：BiFeO in suspension in the step (1)3Concentration is 0.01~0.2mol/L；Stabilizer is second two One kind in amine tetraacethyl disodium, tetrasodium ethylenediamine tetraacetate, sodium gluconate, BTCA, stabilizer concentration is 0.01 ~0.1mol/L.
5. a kind of fiber/CNT/BiFeO according to claim 33The preparation 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/BiFeO according to claim 33The preparation of the recyclable efficient catalytic material of three-dimensional Method, it is characterised in that：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 water of potassium hydroxide Solution.
7. a kind of fiber/CNT/BiFeO according to claim 33The preparation 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, the ratio of H2O2 are 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- perfluor fluorine hexyl iodides are added dropwise over, ultrasonic reaction 18-24h, the quenching that adds water is reacted, washed Wash, dry, obtain product b；Wherein product a, solvent, the ratio of NaH, 1- perfluor fluorine 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/BiFeO according to claim 73The preparation 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/BiFeO according to claim 73The preparation 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/BiFeO as described in claim 1-2 is any3The recyclable efficient catalytic material of three-dimensional Using, it is characterised in that：As the application of water treatment agent, for the treatment of waste water, specially by fiber/CNT/ BiFeO3The recyclable efficient catalytic material of three-dimensional is added in waste water, daylight illumination 3-8h.
CN201611095875.XA 2016-12-02 2016-12-02 A kind of fiber/CNT/BiFeO3Three-dimensional recyclable efficient catalytic material and its preparation and application Pending CN106732795A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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CN107570214A (en) * 2017-10-12 2018-01-12 湖北工业大学 Possesses the preparation method of the paper substrate bismuth ferrite composite of multiphase adsoption catalysis function
CN109772348A (en) * 2017-11-13 2019-05-21 广州中国科学院沈阳自动化研究所分所 A kind of erbium-codoped bismuth ferrite photocatalyst of solid-carrying type copper and its preparation method and application
CN113578368A (en) * 2021-08-29 2021-11-02 蚌埠学院 g-C3N4/Ag3PO4/BiFeO3Preparation method and application of composite visible-light-driven photocatalyst
CN114823153A (en) * 2022-04-24 2022-07-29 华星先进科学技术应用研究(天津)有限公司 Flexible sodium ion capacitor electrode material

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CN104528865A (en) * 2014-12-25 2015-04-22 东华大学 Method for preparing carbon nano tube composite SrFeO3 green deep water treatment agent
CN106040308A (en) * 2016-06-06 2016-10-26 东华大学 Preparation method for textile fiber/graphene/BiFeO3 composite environmental catalytic material

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CN104528865A (en) * 2014-12-25 2015-04-22 东华大学 Method for preparing carbon nano tube composite SrFeO3 green deep water treatment agent
CN106040308A (en) * 2016-06-06 2016-10-26 东华大学 Preparation method for textile fiber/graphene/BiFeO3 composite environmental catalytic material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107570214A (en) * 2017-10-12 2018-01-12 湖北工业大学 Possesses the preparation method of the paper substrate bismuth ferrite composite of multiphase adsoption catalysis function
CN107570214B (en) * 2017-10-12 2020-04-17 湖北工业大学 Preparation method of paper-based bismuth ferrite composite material with multiphase adsorption catalysis function
CN109772348A (en) * 2017-11-13 2019-05-21 广州中国科学院沈阳自动化研究所分所 A kind of erbium-codoped bismuth ferrite photocatalyst of solid-carrying type copper and its preparation method and application
CN113578368A (en) * 2021-08-29 2021-11-02 蚌埠学院 g-C3N4/Ag3PO4/BiFeO3Preparation method and application of composite visible-light-driven photocatalyst
CN113578368B (en) * 2021-08-29 2023-07-07 蚌埠学院 g-C 3 N 4 /Ag 3 PO 4 /BiFeO 3 Preparation method and application of composite visible light catalyst
CN114823153A (en) * 2022-04-24 2022-07-29 华星先进科学技术应用研究(天津)有限公司 Flexible sodium ion capacitor electrode material
CN114823153B (en) * 2022-04-24 2023-11-03 华星先进科学技术应用研究(天津)有限公司 Flexible sodium ion capacitor electrode material

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