CN110004705A - A kind of fabric preparation method with high efficiency photocatalysis function and service graphene - Google Patents
A kind of fabric preparation method with high efficiency photocatalysis function and service graphene Download PDFInfo
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- CN110004705A CN110004705A CN201910170093.5A CN201910170093A CN110004705A CN 110004705 A CN110004705 A CN 110004705A CN 201910170093 A CN201910170093 A CN 201910170093A CN 110004705 A CN110004705 A CN 110004705A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B13/00—Treatment of textile materials with liquids, gases or vapours with aid of vibration
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The present invention provides a kind of fabric preparation method with high efficiency photocatalysis function and service graphene, multi-component high activity composite graphite alkene material batch is carried on the fabric that surface area is big, flexibility is good using infusion process, it comprises the concrete steps that, the titanium-based colloidal sol and silicon substrate colloidal sol of graphene oxide dispersion, doped chemical are first prepared respectively, and the suitable fabric of simultaneous selection is simultaneously pre-processed；Then clean fabric is immersed in GO dispersion liquid and is ultrasonically treated；The titanium-based colloidal sol and silicon substrate colloidal sol of doped chemical are slowly added under ultrasound condition again；Fabric is finally taken out, drying solidifies composite catalyst on the fabric to get the fabric after high efficiency photocatalysis function and service graphene arranges is arrived at a temperature of 50~110 DEG C.Product is greater than 98% to aqueous solution of methylene blue percent of decolourization under visible light, is greater than 99% to the killing rate of bacterium in water, is greater than 98% to the killing rate of Escherichia coli, and photo-catalysis function composite graphite alkene and fabric is firmly combined in sample.
Description
Technical field
The present invention relates to a kind of fabric with high efficiency photocatalysis function and service graphene and preparations, belong to novel nothing
Machine nonmetallic materials technical field.
Technical background
Photocatalysis be used to degrade environmental contaminants be one developing and improving in new technology, but with TiO2For generation
Although traditional photochemical catalyst chemical property of table is stablized, use is safe, and cost is relatively low, they need wavelength 387nm below
Ultraviolet excitation, and the light induced electron (e generated-) and photohole (h+) be easy to compound, imitate the quantum of light-catalyzed reaction
Rate is very low, can not utilize visible light, then having is exactly powdery photocatalyst difficult recycling etc. in waste water and exhaust-gas treatment, thus
Limit the application of the technology.For these defects, various R&D works are carried out both at home and abroad, such as in TiO2Modification side
Face take noble metal loading, by several semiconductors couplings, ion doping, photosensitizer and surface reduction processing etc.；In photocatalysis
Aspect is coupled with other technologies, then takes microwave field and help photocatalysis, thermocatalytic and photocatalysis coupled and photocatalysis and electro-catalysis
Coupling etc..
Graphene has the excellent performances such as electron mobility is high, Young's modulus is high, the high and easy chemistry functional of intensity,
Derivative has graphene oxide and redox graphene etc..Due to specific physical and chemical property that they have, at
For a kind of new material of materials science field, it is possible to solve the problems, such as that traditional photochemical catalyst faces.It is some studies have shown that will
The composite photo-catalyst of graphene or derivative, modification (is such as spun by being either physically or chemically carried on some carrier materials
Fabric, metal mesh, porous ceramics etc.), so that it may expand the range that catalyst utilizes visible light, improves light and urge depollution and kill
The efficiency of bacterium, the more convenient sewage and air cleaning in various occasions of product.
Have many related reports in recent years, representative paper has " graphene/TiO2Composite material photocatalytic degradation has
The progress of machine pollutant " (Journal of Chemical Industry and Engineering, Vol.67No.5).This article thinks that graphene is a kind of novel carbon nanometer material
Material, specific surface area and excellent electric conductivity with super large, by graphene and TiO2The compound composite material of being remarkably improved
Photocatalysis performance is with a wide range of applications in photocatalysis field.This article describes graphene/TiO2Composite nano materials
Preparation method and the application in terms of photocatalysis degradation organic contaminant, and analyze graphene/TiO2Composite material promotes
Photocatalytic mechanism, finally to graphene/TiO2The development trend in composite photo-catalyst future proposes prospect.Related invention is special
Benefit is also more, such as:
CN109092279A discloses a kind of highly effective cellulose base class graphene/TiO2Composite photo-catalyst and its preparation side
Method impregnates in Ni solution after carbonizing cellulose, carries out graphitization reaction under high temperature after dry, further uses
Hummers method aoxidizes product, and is scattered in aqueous solution under ultrasonication, sequentially adds H3BO3(NH4)2TiF6, water
Solution, is then calcined at a certain temperature, and cellulose base class graphene/TiO is made2Composite photo-catalyst.The invention is with cellulose
For raw material, cellulose base class graphene/TiO has been made by catalyzed graphitization-oxidation-deposition-reduction2Composite photo-catalyst,
But it is at high cost.The photochemical catalyst has high photocatalytic activity, under the irradiation of ultraviolet light can be in 8 minutes by 10mg/L's
The Cr (VI) that concentration is 0.2mmol/L completely, can be reduced to Cr in 30 minutes by methyl orange solution degradation3+。
CN106040311A discloses a kind of textile fabric/graphene/FeVO4The preparation side of combinational environment catalysis material
Method, comprising: textile fabric is impregnated into the saturation dispersion liquid of graphene oxide, is then dried, cleans, is subsequently placed in reducing agent
In solution, 50~80 DEG C of 0.5~1h of reaction are cleaned, and drying obtains textile fabric/graphene；Textile fabric/graphene is added
Enter to Fe (NO3)3And Na3PO4In solution, then NaVO is added in stirring3And urea, 120~180 DEG C of hydro-thermal reaction 3~8h are cold
But it washs afterwards, dries, obtain textile fabric/graphene/FeVO4Combinational environment catalysis material.Catalyst is easy to fall off, in practical
It is easy to be restricted.
CN109043681A discloses a kind of Graphene antibiosis fiber body shaping underwear, and there is no in Combined undergarment inconvenience for it
The shortcomings that lavatory, will not scroll up, and have comfortable and easy to wear, conveniently, the good feature of moulding effect；And it is mixed using a kind of europium
Miscellaneous Graphene antibiosis fiber cloth is made, and has good antibacterial effect, wears next to the skin also very hygienic and safe.
Summary of the invention
The purpose of the present invention: it is intended to provide a kind of graphene/composite Ti O of visible light-responded catalysis2/ scrim
Material and preparation with organic pollutant in the useless water and air of, removal big to visible light-responded range and kill bacterium
Activity it is high, easy to use and service life is long, at low cost the features such as, to promote photocatalysis technology in environmental pollution improvement
Practical application.
The technical scheme is that a kind of fabric and preparation with high efficiency photocatalysis function and service graphene,
Multi-component high activity composite graphite alkene material batch is carried on by the fabric that surface area is big, flexibility is good using infusion process
On, it comprises the concrete steps that, first prepare the titanium-based colloidal sol and silicon substrate colloidal sol of GO dispersion liquid, doped chemical respectively, simultaneous selection fiber is knitted
Object is simultaneously pre-processed；Then clean fabric is immersed in GO dispersion liquid and is ultrasonically treated；Again under ultrasound condition
It is slowly added to the titanium-based colloidal sol and silicon substrate colloidal sol of doped chemical；Fabric is finally taken out, drying at a temperature of 50~110 DEG C makes
Composite catalyst solidifies to arrive the fabric after high efficiency photocatalysis function and service graphene arranges on the fabric.
GO dispersion liquid is prepared using improved Hummers method: in dense H under low temperature and agitating state2SO4Middle addition scale
Graphite powder, then it is respectively added slowly to strong oxidizer and deionized water, continue to stir, reducing agent is added under medium temperature, becomes to reaction solution
To filter while hot after glassy yellow, it is neutral for being washed respectively with diluted acid and deionized water to filtrate, then obtained graphite oxide is divided
It dissipates in deionized water and disperses under ultrasound condition, as GO dispersion liquid.
Used strong oxidizer is K when the preparation of GO dispersion liquid2Cr2O7、KClO3、KMnO4And HClO, reducing agent are
Na2S2O3、(NH4)2Fe(SO4)2, ascorbic acid and H2O2, diluted acid HCl, acetic acid, the wherein mass ratio of raw material are as follows: crystalline flake graphite
Powder: the concentrated sulfuric acid: oxidant: reducing agent: diluted acid: deionized water=1.5~2.5: 90~100: 2.8~3.6: 2.5~3.2:
0.02~0.2: 350~450.
Further, it prepares the titanium-based colloidal sol of doped chemical: titanate esters is slowly added to the mixing of dehydrated alcohol and glacial acetic acid
In solution, solution A is obtained；The nitrate of doped chemical is dissolved in dehydrated alcohol and deionized water, solution B is obtained；It again will be molten
Liquid A is slowly added dropwise into the solution B for being placed in ice-water bath, is stirred continuously the titanium-based colloidal sol adulterated.Prepare the titanium of doped chemical
When based sols, the mass ratio of solution A are as follows: titanate esters: dehydrated alcohol: glacial acetic acid=11.5~23.0: 51.9~65.1: 0.7~
7.1, the titanate esters of use are positive titanium propanolate or positive butyl titanate；The mass ratio of solution B are as follows: doped chemical nitrate: anhydrous
Ethyl alcohol: deionized water=0.2~0.8: 14.8~26.1: 0.7~3.5, the doped chemical used is first for La, Ce, Pm and Sm etc.
The nitrate of element；Finally obtain doping TiO2Colloidal sol.
Preparation silicon substrate colloidal sol: positive esters of silicon acis is slowly added in dehydrated alcohol, deionized water and diluted acid mixed solution, is stirred
It is uniformly mixed, mass ratio are as follows: positive esters of silicon acis: dehydrated alcohol: deionized water: diluted acid=4.5~4.8: 9.2~11.8: 1.5~
2.0: 0.02~0.04；The esters of silicon acis used is ethyl orthosilicate or positive silicic acid propyl ester, and the diluted acid used is HCl, acetic acid etc.；?
To SiO2Colloidal sol.
For the fabric used for pure cotton fabric or polyester-cotton fabric, fabric need to be molten with NaOH and synthetic detergent in advance
Liquid boiling is boiled, then is washed to neutrality after being neutralized with glacial acetic acid, is dried for standby.
GO dispersion liquid, doped chemical titanium-based colloidal sol and silica solution is implemented step by step using infusion process to load on fabric:
I.e. in ultrasonic oscillation system, first pretreated sheet-like fiber fabric is placed in GO dispersion liquid, is then slowly added into and mixes
The titanium-based colloidal sol and silicon substrate colloidal sol of miscellaneous element, finally take out fabric, dry at a certain temperature and solidify composite catalyst.
It is loaded on fabric using graphene oxide, doped chemical titanium-based colloidal sol and silicon substrate colloidal sol is implemented step by step, institute
With the mass ratio of primary raw material are as follows: GO dispersion liquid: doped chemical titanium-based colloidal sol: silicon substrate colloidal sol: fabric=403.2~
458.6: 93.4~109.1: 14.3~18.9: 30.4~250.1.
Beneficial effects of the present invention: the present invention strictly select raw material and concentration proportioning, ultrasonic intensity and ultrasonic time,
And under the process conditions such as day part temperature and pH value of solution, a kind of fibre with high efficiency photocatalysis function and service graphene has been made
Fabric is tieed up, obviously effect is achieved.First is that substantially increasing the photocatalysis efficiency of organic pollutant degradation；Second is that this is urged
Agent has widened the response range to visible light；Third is that having selected the fabric that surface area is big, flexibility is good as high activity
The carrier of composite graphite alkene is allowed to be firmly combined, and service life is long.Therefore, the present invention can promote using the sun administer exhaust gas and
Waste water, it will generate good economic and social benefit.Decoloration of the inventive article to aqueous solution of methylene blue under visible light
Rate is greater than 98%, is greater than 99% to the killing rate of bacterium in water, is greater than 98% to the killing rate of Escherichia coli, in the sample of preparation
Photo-catalysis function composite graphite alkene and fabric are firmly combined, and it is several to reuse 10 its aqueous solution of methylene blue percent of decolourizations
It is constant.
Specific embodiment
1, the material needed for preparing and pre-process
(1) GO dispersion liquid is prepared using improved Hummers method: crystalline graphite powder is added under low temperature and agitating state
Dense H2SO4In, then it is respectively added slowly to strong oxidizer and deionized water, continue to stir, reducing agent is added under medium temperature, to reaction solution
It is filtered while hot after becoming glassy yellow, it is neutral for being washed respectively with diluted acid and deionized water to filtrate, then the graphite oxide that will be obtained
It is scattered in deionized water and disperses under ultrasound condition, as GO dispersion liquid.Oxidant used in it is KClO3Or
KMnO4, reducing agent is ascorbic acid and H2O2, diluted acid is dilute hydrochloric acid or acetic acid etc..
(2) it prepares the titanium-based colloidal sol of doped chemical: titanate esters is slowly added to the mixed solution of dehydrated alcohol and glacial acetic acid
In, obtain solution A；The nitrate of doped chemical is dissolved in dehydrated alcohol and deionized water, solution B is obtained；Solution A is delayed again
Slowly it is added dropwise in the solution B for being placed in ice-water bath, is stirred continuously the TiO adulterated2Colloidal sol.Titanate esters used in it, doping
The type of element nitrate is specific, raw materials used to have certain proportion.
(3) it prepares silicon substrate colloidal sol: positive esters of silicon acis is slowly added in dehydrated alcohol, deionized water and diluted acid mixed solution,
It is uniformly mixed, obtains SiO2Colloidal sol.Wherein esters of silicon acis used is ethyl orthosilicate or positive silicic acid propyl ester, its raw materials used matter
Measure ratio are as follows: positive esters of silicon acis: dehydrated alcohol: deionized water: diluted acid=4.5~4.8: 9.2~11.8: 1.5~2.0: 0.02~
0.04。
(4) select fabric and pretreatment: the fabric used is pure cotton fabric or polyester-cotton fabric or natural fiber
With the various blended fabric of staple fibre, first by fabric and alkali (such as Na2CO3, NaOH etc.) and synthesis of detergent agent solution boiling
It boils, then is washed to neutral (pH value is 6.5~7.5) after being neutralized with glacial acetic acid, be dried for standby.
2, various composition is implemented step by step on fabric using infusion process to load
(1) fabric after pretreatment is immersed in graphene oxide solution and is ultrasonically treated.
(2) under ultrasound condition, it is slowly added to the titanium-based colloidal sol of doped chemical.
(3) under ultrasound condition, it is slowly added to silicon substrate colloidal sol.
(4) fabric is finally taken out, is dried at 50~110 DEG C and solidifies composite catalyst to get required product is arrived.
3, product physicochemical property characterizes
(1) with ultraviolet-visible diffuse reflectance spectrum instrument measurement sample to the absorption region of light, according to Eg=1240/ λ formula is estimated
Calculate the band gap of semiconductor.
(2) unsupported polyester-cotton fabric and load methylene blue light degradation percent of decolourization: are put into 2 culture dishes respectively
Fabric, it is each that the methylene blue solution that 50ml concentration is 20mg/l is added, culture dish is placed in illumination (wavelength under the fluorescent lamp of 20W
For 400nm~760nm), liquid level is apart from light source center 25cm, different time sampling, with ultraviolet-visible spectrophotometer in wavelength
The absorbance change that methylene blue solution is measured at 650nm, is mapped with the variable quantity of solution absorbance and light application time relationship, can
The percent of decolourization of different periods methylene blue is obtained, can indicate the photocatalytic activity of this fabric.
(3) sterilization test: flat band method measures sample in GB5750-85 " drinking water standard method of inspection " according to national standards
The killing bacteria effect of product is gone out rate according to the bacterium of MTF method measurement large intestine bar in the standard.
(4) fastness to washing: according to GB/T3921-2008 " textile color stability test fastness to soaping ", after arrangement
Fabric carry out soaping for 30 times respectively, pass through illumination before and after methyl blue solution absorbance change evaluation fabric washability.
(5) it reuses the service life: fabric being put into methylene blue solution and carries out for the first time after the test, taking out again
It is put into new methylene blue solution and carries out second of test, be so repeated as many times, investigate the service life of fabric.
Embodiment 1:Ce adulterates TiO2/SiO2The preparation and performance of/GO/ polyester-mixed cotton cloth
Ce doping TiO is made according to above embodiment2/SiO2/ GO/ polyester-mixed cotton cloth 40, preparation method and sample detection knot
Fruit is as follows:
(1) it prepares GO dispersion liquid: the 60ml concentrated sulfuric acid being added in the three-necked flask of ice-water bath, is added with stirring 2.5g graphite
Powder stirs 15h at room temperature.It is slow added into 4g potassium permanganate, control reaction temperature is no more than 10 DEG C, after 20min, when being warming up to
50 DEG C, continue to stir 3h, be slow added into the deionized water of 110ml, continue to stir 20min, when being warming up to 90 DEG C, is added
12ml, the hydrogen peroxide that mass fraction is 30%, are filtered after reaction solution becomes glassy yellow, and with 5%HCl solution and deionized water
Filtrate is washed to neutrality.It disperses obtained graphite oxide in 300ml aqueous solution, disperses 1h under ultrasound condition, obtain steady
Fixed GO dispersion liquid.
(2) preparation Ce adulterates TiO2Colloidal sol: tetrabutyl titanate is slowly added to the mixed solution of dehydrated alcohol and glacial acetic acid
In, titanium N-butyl: dehydrated alcohol: glacial acetic acid=17.5: 62.1: 3.7, obtain solution A；By Ce (NO3)3·6H20 is dissolved in nothing
In water-ethanol and deionized water, Ce (NO3)3·6H20: dehydrated alcohol: deionized water=0.5: 20.8: 2.1, obtain solution B；
Solution A is slowly added dropwise into the solution B for being placed in ice-water bath again.
(3) SiO is prepared2Colloidal sol: by the ethyl orthosilicate of 5ml be slowly added to 15ml dehydrated alcohol, 2ml deionized water and
In the HCl mixed solution of 0.05ml, magnetic agitation 2h is uniformly mixed.
(4) polyester-cotton fabric pre-processes: polyester-mixed cotton cloth fabric being cut into 100mm × 40mm coupon, with the NaOH of concentration 5g/l
It is boiled at 80~90 DEG C with the synthetic detergent of 4g/l and boils 30min, then neutralized with glacial acetic acid, be washed to neutrality, 90 DEG C of drying are standby
With.
(5) GO dispersion liquid, Ce doping TiO are implemented step by step2Colloidal sol and SiO2Colloidal sol loads on polyester-mixed cotton cloth: after pretreatment
40 pieces of 100mm × 40mm polyester-mixed cotton cloth be impregnated in the GO dispersion liquid of 300ml, ultrasonic 1.5h；It is slowly dripped under ultrasound condition again
Enter the TiO of 50ml doping Ce2Colloidal sol controls 65 DEG C of temperature or so ultrasound 2h；It is slowly dropped into 19.7ml's under ultrasound condition again
SiO2Colloidal sol continues ultrasound 2h at 65 DEG C；Fabric is finally taken out, 5min is dried at 80 DEG C, solidifies 1h at 120 DEG C to get arriving
Product.
(6) sample detection result
1. the test of ultraviolet-visible diffuse reflectance spectrum instrument shows that sample is super to the strong absorption region of light to the absorption region of light
510nm is crossed, sideband expands to 650nm, according to Eg=1240/ λ estimation, band gap are reduced to 2.0eV or so.
2. light degradation experiments have shown that, under the radiation of visible light of 8h, 98% is reached to the percent of decolourization of methylene blue.
3. impregnating sterile test for 24 hours to show when total number of bacteria is 2900/ml, Escherichia coli are 790 bacterium in water sample
At group/100ml milliliters, 99% or more is reached to the sterilization rate of bacterium, 95% is greater than to the sterilization rate of Escherichia coli.
4. fastness to washing test shows: the methylene blue solution absorbance for impregnating unsupported fabric has almost no change, and
The methylene blue solution absorbance for impregnating fabrics is 95% to the degradation rate of methylene blue, after 30 washings, degradation
Rate still reaches 94.3%, shows that load fastness is strong, washability is good.
5. service life experiments have shown that: sample reuse 10 times after, through visible light shine 8h, the color of methylene blue solution
It still almost takes off and illustrates that prepared photocatalysis coating fabric is reusable only, and service life is longer.
Embodiment 2:Ce adulterates TiO2The preparation of/GO/ polyester-mixed cotton cloth and performance (also making 40)
Except step (3) does not prepare SiO in embodiment 12Colloidal sol and step (5) do not load SiO2Outside colloidal sol, remaining operating procedure
It is same as Example 1.Test result is as follows for sample:
1. the test of ultraviolet-visible diffuse reflectance spectrum instrument shows that sample is super to the strong absorption region of light to the absorption region of light
510nm is crossed, sideband expands to 650nm.
2. light degradation experiments have shown that, be 92% to the percent of decolourization of methylene blue under the radiation of visible light of 8h.
3. impregnating sterile test for 24 hours to show when total number of bacteria is 2900/ml, Escherichia coli are 790 bacterium in water sample
At group/100ml milliliters, 95% is greater than to the sterilization rate of bacterium, 90% is greater than to the sterilization rate of Escherichia coli.
4. fastness to washing test shows: the methylene blue solution absorbance for impregnating unsupported fabric has almost no change, and
The methylene blue solution absorbance for impregnating fabrics is 92% to the degradation rate of methylene blue.After 30 washings, degradation
Rate still reaches 91.5%, shows that washability is good.
5. service life experiments have shown that: the fabrics reuse 10 times after, through visible light shine 8h, methylene blue solution
Percent of decolourization only reduce by 3.5%, illustrate that prepared photocatalysis coating fabric is reusable and service life is longer.
Embodiment 3:Ce adulterates TiO2/SiO2The preparation of polyester-mixed cotton cloth and performance (also making 40)
Except step (1) does not prepare preparation GO dispersion liquid and in addition to step (5) do not load GO dispersion liquid in embodiment 1, remaining behaviour
It is same as Example 1 to make step.Test result is as follows for sample:
1. the test of ultraviolet-visible diffuse reflectance spectrum instrument shows that sample is super to the strong absorption region of light to the absorption region of light
500nm is crossed, sideband expands to 630nm.
2. light degradation experiments have shown that, be 88% to the percent of decolourization of methylene blue under the radiation of visible light of 8h.
3. impregnating sterile test for 24 hours to show when total number of bacteria is 2900/ml, Escherichia coli are 790 bacterium in water sample
At group/100ml milliliters, 90% is greater than to the sterilization rate of bacterium, 85% is greater than to the sterilization rate of Escherichia coli.
4. fastness to washing test shows: the methylene blue solution absorbance for impregnating unsupported fabric has almost no change, and
The methylene blue solution absorbance for impregnating fabrics is 92% to the degradation rate of methylene blue.After 30 washings, degradation
Rate still reaches 91.5%, shows that washability is good.
5. service life experiments have shown that: the fabrics reuse 10 times after, through visible light shine 8h, methylene blue solution
Percent of decolourization only reduce by 3.5%, illustrate that prepared photocatalysis coating fabric is reusable and service life is longer.
Embodiment 4:TiO2/SiO2The preparation of/GO/ polyester-mixed cotton cloth and performance (also making 40)
Except step (2) preparation Ce adulterates TiO in embodiment 12Ce (NO is not added in colloidal sol3)3·6H2Outside 0, remaining operation step
It is rapid same as Example 1.Test result is as follows for sample:
1. the test of ultraviolet-visible diffuse reflectance spectrum instrument shows that sample is super to the strong absorption region of light to the absorption region of light
510nm is crossed, sideband expands to 650nm.
2. light degradation experiments have shown that, be 92% to the percent of decolourization of methylene blue under the radiation of visible light of 8h.
3. impregnating sterile test for 24 hours to show when total number of bacteria is 2900/ml, Escherichia coli are 790 bacterium in water sample
At group/100ml milliliters, 95% is greater than to the sterilization rate of bacterium, 90% is greater than to the sterilization rate of Escherichia coli.
4. fastness to washing test shows: the methylene blue solution absorbance for impregnating unsupported fabric has almost no change, and
The methylene blue solution absorbance for impregnating fabrics is 92% to the degradation rate of methylene blue.After 30 washings, degradation
Rate still reaches 91.5%, shows that washability is good.
5. service life experiments have shown that: the fabrics reuse 10 times after, through visible light shine 8h, methylene blue solution
Percent of decolourization only reduce by 3.5%, illustrate that prepared photocatalysis coating fabric is reusable and service life is longer.
Above-described embodiment shows that GO dispersion liquid, Ce are adulterated TiO using infusion process2Colloidal sol and SiO2Colloidal sol step load in
(see embodiment 1) on polyester-mixed cotton cloth, product is very high to the Photocatalytic Decoloration efficiency of representative methylene blue organic matter,
It is also very high to the activity for killing bacterium and Escherichia coli；And such as lack GO (see embodiment 2), SiO in product2(see embodiment 3)
With doped chemical Ce (see embodiment 4), then the photocatalysis of product and bactericidal activity will decline to some extent, but all implementations
The service life variation of the compound and polyester-mixed cotton cloth binding strength and sample of example preparation is little.
Claims (9)
1. the fabric preparation method after a kind of arrangement with high efficiency photocatalysis function and service graphene, characterized in that use
Multi-component high activity composite graphite alkene material batch is carried on the fabric that surface area is big, flexibility is good by infusion process,
It comprises the concrete steps that, first prepare the titanium-based colloidal sol and silicon substrate colloidal sol of graphene oxide dispersion, doped chemical respectively, simultaneous selection is closed
Suitable fabric is simultaneously pre-processed；Then clean fabric is immersed in GO dispersion liquid and is ultrasonically treated；Exist again
The titanium-based colloidal sol and silicon substrate colloidal sol of doped chemical are slowly added under ultrasound condition；Fabric is finally taken out, in 50~110 DEG C of temperature
Drying under degree solidifies composite catalyst on the fabric knits to get the fiber after arranging to high efficiency photocatalysis function and service graphene
Object.
2. preparation method according to claim 1, characterized in that prepare GO dispersion liquid using improved Hummers method:
In dense H under low temperature and agitating state2SO4Crystalline graphite powder is added, then is respectively added slowly to strong oxidizer and deionized water, continues
Stirring is added reducing agent under medium temperature, filters while hot after reaction solution becomes glassy yellow, respectively with diluted acid and deionized water wash to
Filtrate is neutrality, then disperses obtained graphite oxide in deionized water and disperse under ultrasound condition, as GO dispersion liquid.
3. preparation method according to claim 2, characterized in that used strong oxidizer is when the preparation of GO dispersion liquid
K2Cr2O7、KClO3、KMnO4And HClO, reducing agent Na2S2O3、(NH4)2Fe(SO4)2, ascorbic acid and H2O2, diluted acid HCl,
Acetic acid, the wherein mass ratio of raw material are as follows: crystalline graphite powder: the concentrated sulfuric acid: oxidant: reducing agent: diluted acid: deionized water=1.5~
2.5: 90~100: 2.8~3.6: 2.5~3.2: 0.02~0.2: 350~450.
4. according to claim 1, preparation method described in 2, characterized in that prepare the titanium-based colloidal sol of doped chemical: by titanate esters
It is slowly added in the mixed solution of dehydrated alcohol and glacial acetic acid, obtains solution A；The nitrate of doped chemical is dissolved in dehydrated alcohol
In deionized water, solution B is obtained；Solution A is slowly added dropwise into the solution B for being placed in ice-water bath again, is stirred continuously and is mixed
Miscellaneous titanium-based colloidal sol.
5. preparation method according to claim 4, characterized in that when preparing the titanium-based colloidal sol of doped chemical, the quality of solution A
Than are as follows: titanate esters: dehydrated alcohol: glacial acetic acid=11.5~23.0: 51.9~65.1: 0.7~7.1, the titanate esters of use are positive
Titanium propanolate or positive butyl titanate；The mass ratio of solution B are as follows: doped chemical nitrate: dehydrated alcohol: deionized water=0.2~
0.8: 14.8~26.1: 0.7~3.5, the doped chemical used is the nitrate of the elements such as La, Ce, Pm and Sm；It finally obtains and mixes
Miscellaneous TiO2Colloidal sol.
6. preparation method according to claim 1, characterized in that positive esters of silicon acis preparation silicon substrate colloidal sol: is slowly added to nothing
It in water-ethanol, deionized water and diluted acid mixed solution, is uniformly mixed, mass ratio are as follows: positive esters of silicon acis: dehydrated alcohol: going
Ionized water: diluted acid=4.5~4.8: 9.2~11.8: 1.5~2.0: 0.02~0.04；The esters of silicon acis used is ethyl orthosilicate
Or positive silicic acid propyl ester, the diluted acid used is HCl, acetic acid etc.；Obtain SiO2Colloidal sol.
7. preparation method according to claim 1, characterized in that the fabric used is knitted for pure cotton fabric or polyester-cotton blend
Object, fabric needs to be boiled with NaOH and the boiling of synthesis of detergent agent solution in advance, then neutrality is washed to after being neutralized with glacial acetic acid, dries standby
With.
8. preparation method according to claim 1, characterized in that implement GO dispersion liquid, doping member step by step using infusion process
Plain titanium-based colloidal sol and silica solution load on fabric: first that pretreated sheet is fine i.e. in ultrasonic oscillation system
Dimension fabric is placed in GO dispersion liquid, is then slowly added into the titanium-based colloidal sol and silicon substrate colloidal sol of doped chemical, is finally taken out fabric,
It is dried under specific temperature and solidifies composite catalyst.
9. preparation method according to claim 8, characterized in that use and implement graphene oxide, doped chemical titanium step by step
Based sols and silicon substrate colloidal sol load on fabric, the mass ratio of primary raw material used are as follows: GO dispersion liquid: doped chemical titanium-based
Colloidal sol: silicon substrate colloidal sol: fabric=403.2~458.6: 93.4~109.1: 14.3~18.9: 30.4~250.1.
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