CN101851343A - Composite film with photocatalytic oxidability and preparation method thereof - Google Patents
Composite film with photocatalytic oxidability and preparation method thereof Download PDFInfo
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- CN101851343A CN101851343A CN 201010176850 CN201010176850A CN101851343A CN 101851343 A CN101851343 A CN 101851343A CN 201010176850 CN201010176850 CN 201010176850 CN 201010176850 A CN201010176850 A CN 201010176850A CN 101851343 A CN101851343 A CN 101851343A
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Abstract
The invention discloses a composite film with photocatalytic oxidability and a preparation method thereof. The preparation method comprises the following steps: preparing titanium dioxide/carbon nanotube powder through glue melting and condensation, and uniformly dispersing the titanium dioxide/carbon nanotube composite material into acetic acid solution of chitosan with the chitosan as a crosslinking agent, wherein the mass ratio of the chitosan and the titanium dioxide/carbon nanotube is 1 to 10, thereby obtaining the catalytic film made of titanium dioxide/carbon nanotube/chitosan material. The composite film prepared in the method is uniform, the preparation method is simple, the raw materials are cheap, and the sources are rich. The defect structure of the surface of the raw carbon nanotube provides growing points for the growth of titanium dioxide grains. In addition, the adsorbed organic substances and intermediates of photodegradation have the function of coordinating with functional groups of the chitosan. The composite catalytic film provided by the invention can be used for photocatalytic oxidation of volatile organic compounds (VOCs) under the visible light irradiation with the wavelength more than 350nm, and can be used as the air purification agent, the industrial waste water treatment agent and the like.
Description
Technical field
The present invention relates to a kind of carbon nano-tube/titanic oxide/chitosan laminated film and preparation method thereof, belong to the preparation and the applied technical field of nano-photocatalyst with photocatalytic-oxidation voltinism.
Background technology
Indoor volatile organic compounds (VOCs) removal method mainly contains active carbon adsorption, plant purification, electrostatic precipitation, photochemical catalysis etc.Photochemical catalysis has at present become the research focus in indoor air quality field as a kind of new technology, and photocatalyst material can produce free electron (e under the irradiation of ultraviolet ray (UV)
-) and hole (h
+), oxidable decomposing organic compounds and part inorganics, and have functions such as extremely strong antifouling, sterilization and deodorizing.
TiO
2Photocatalysis oxidation technique is based upon on the N-type semiconductor band theory basis, its essence is in photoelectricity transforms to carry out redox reaction.During the rayed TiO 2 particles, electronics from the valence to the conduction band on the time, on valence band, stay the hole, form light induced electron-hole to (e
-h
+).e
-With h
+The different positions of separated migrates to the particle grain takes place, thus the photic electronics e on the conduction band
-Have very strong activity, formed redox system at titanium dioxide surface; On valence band, form photo-induced hole h simultaneously
+, the photo-induced hole on the valence band has strong oxidizing property, and the oxidation capacity of the hydroxyl radical free radical (OH) that produces with airborne moisture and oxygen generation redox reaction is very strong, and free-radical oxidn decomposes VOCs, generates CO
2And H
2O, but e
-With h
+Also surface recombination can take place, cause the photocatalytic degradation ability to reduce.
Zhi Bei composite catalyst mainly contained two classes in the past, and a class is the carbon nano-tube/titanic oxide matrix material, and the matrix material of preparation is Powdered, and reacted catalyst separating and recovery difficulty, and a reunion in water lose activity.Another kind of is the preparation of titanium dioxide/chitosan matrix material, this method because of the photocatalytic degradation of preparation to the having relatively high expectations of light, and because the specific surface area of the matrix material of preparation is little, the catalytic effect of catalysis pollutent is undesirable.
Summary of the invention
The object of the present invention is to provide a kind of carbon nano-tube/titanic oxide/chitosan laminated film and preparation method thereof with photocatalytic-oxidation voltinism.Carbon nano-tube/titanic oxide/chitosan the laminated film that adopts the inventive method preparation is in conjunction with strong, that higher visible light catalytic oxidation activity is arranged carbon nano-tube/titanic oxide/chitosan laminated film between a kind of carbon nanotube and the titanium dioxide nano-particle.And this preparation method is easy and simple to handle, and cost is low, and product has higher thermostability and excellent visible light catalytic oxidation activity.
Technical scheme provided by the invention is:
A kind of preparation method: the mass ratio 1: 10 of pressing chitosan and carbon nano-tube/titanic oxide composite granule with laminated film of photocatalytic-oxidation voltinism, the carbon nano-tube/titanic oxide composite granule is added in the 1wt% acetic acid solution of 10ml chitosan, and stir, obtain mucus; Then mucus is coated with and is plated on the carrier, 80 ℃ of dryings are 1 day in 4 hours rearmounted loft drier of drying at room temperature, eliminate residual moisture and acetate, promptly get described laminated film.
The preparation process of described carbon nano-tube/titanic oxide composite granule is specific as follows:
1) gets the tetrabutyl titanate of 5ml and the dehydrated alcohol of 10ml and place the beaker of 20ml, and stir 30min, obtain water white solution; In the dehydrated alcohol of 10ml, ultra-sonic dispersion 15min obtains homodisperse suspension with the carbon nanotube ultra-sonic dispersion of 0.0112-0.112g 40-60nm;
2) the dehydrated alcohol dispersion liquid of the carbon nanotube that step 1) is obtained dropwise is added in the ethanol solution of the tetrabutyl titanate that step 1) obtains and stirs, and drop rate is 0.5 droplet/second, drips the back and continues violent stirring 30min, obtains even mixed solution;
3) with syringe the acetic acid solution of 1.5ml dropwise being added to step 2 then) in the mixing solutions that obtains and stir, the mol ratio of acetate and water is 0.055: 1; 0.2 droplet/second of rate of addition drips the back and continue to stir 30min, obtains the colloidal sol of titanium dioxide/carbon nanotube, drying at room temperature then, and ageing 4d obtains the xerogel of titanium dioxide/carbon nanotube;
4) xerogel is placed 60 ℃ of dry 12h of loft drier, grind with mortar then, be ground to powder and get final product, again powder is placed 450 ℃ of calcinations of retort furnace, heat up, make titanium dioxide/carbon nano-tube composite powder to 2-3 ℃/min.
Experiment shows, the present invention proposes the carbon nano-tube/titanic oxide matrix material of preparation is joined in the acetic acid solution of chitosan, the matrix material catalytic film of preparing has good photocatalytic activity, main because following some: (1) carbon nanotube of the present invention does not need further purifying, reduced the loss of raw material, directly utilize the defect structure on the surface of primary carbon nanotube to provide vegetative point, help the outer wall that titania is wrapped in carbon nanotube for the growth of titania; Both well combine, and are beneficial to light-catalyzed reaction, and carbon nanotube is the big tubular structure of specific surface area, so organism is had good adsorptivity; In addition, the surface imperfection of carbon nanotube and conductivity suppress the compound of electron-hole pair, have also just suppressed the reduction of photocatalytic degradation ability; (2) organism that is adsorbed and the intermediate product in the photodegradation and the functional group in the chitosan have produced coordinative role, are because in the chitosan active group amino (NH is arranged on the one hand
2-) and hydroxyl (OH-), intermediate product that produces in organism and the photodegradation process and the active group in the chitosan are adsorbed on the surface of catalyzer by intermolecular reactive force with organism and intermediate product, help light-catalyzed reaction; On the other hand, for light-catalyzed reaction, catalyzed reaction mainly is the comprehensive competing reaction that occurs in catalyst surface, thereby, the surface characteristic of catalyzer, as: surface acidity, defective and hydroxyl can both influence reaction efficiency, and having the greatest impact of hydroxyl wherein, thereby water molecules is very important for light-catalyzed reaction, chitosan is as a kind of polysaccharide, have good wetting ability, reactive behavior is improved so the adding of chitosan also helps photochemical catalysis; And chitosan has good film forming properties, thereby chitosan is added in the light-catalysed matrix material, easily makes large-area photocatalysis thin film.
Description of drawings
Fig. 1 is fourier infrared (FT-IR) the spectroscopic analysis collection of illustrative plates of the titanium dioxide/carbon nanotube/chitosan matrix material catalytic film of carbon nano-tube/titanic oxide and gained of the present invention;
Wherein a is a chitosan, and b is and the titanium dioxide/carbon nanotube/chitosan matrix material catalytic film of gained of the present invention that c is a carbon nano-tube/titanic oxide.
The characteristic peak that can observe chitosan corresponding in titanium dioxide/carbon nanotube/chitosan film from Fig. 1 fails gradually, between functional group in the chitosan and the titanium dioxide/carbon nano tube compound material due to the coordinative role, thus the photocatalytic activity of reinforced composite film.
Fig. 2 is that the XRD (X-ray diffraction) of carbon nano-tube/titanic oxide and gained titanium dioxide/carbon nanotube of the present invention/chitosan matrix material catalytic film analyzes collection of illustrative plates.
Wherein a is gained titanium dioxide/carbon nanotube of the present invention/chitosan matrix material catalytic film, and b is a carbon nano-tube/titanic oxide, and c is a chitosan;
As can be seen from Figure 2 diffraction peak (101), (004), (200) show as typical anatase octahedrite facies pattern with (204), and no rutile facies pattern illustrates that the titanium dioxide of preparation has good photocatalytic.Adopt the Scherrer formula to calculate the crystal grain of the titanium dioxide that this experiment sol-gel prepares between 10-20nm.
Fig. 3 is transmission electron microscope (TEM) photo of titanium dioxide/carbon nanotube of the present invention/chitosan matrix material catalytic film.
As can be seen from Figure 3 granular TiO 2 particles is wrapped in the surface of carbon nanotube, illustrates that the defect point of primary carbon nano tube surface becomes the vegetative point of titanium dioxide nucleus, thereby causes a large amount of titanium dioxide granules to be grown on the carbon nanotube outer wall; And chitosan is dispersed in titanium dioxide/carbon nanotube in the matrix of chitosan as linking agent, helps the formation of matrix material catalysis rete.
Fig. 4 is the nano-composite catalyst of the present invention of carbon nano-tube/titanic oxide of different content and the ultraviolet-visible light total reflection spectrogram of commercial P25 type titanium dioxide.
A titanium dioxide/carbon nanotube (10%)/chitosan matrix material catalytic film of being wherein, b is titanium dioxide/carbon nanotube (5%)/chitosan matrix material catalytic film, c is titanium dioxide/carbon nanotube (2%)/chitosan matrix material catalytic film, d is titanium dioxide/carbon nanotube (1%)/chitosan matrix material catalytic film, and e is the titanium dioxide of commercial P25 type.
As can be seen from Figure 4 the electronic band gap of matrix material of the present invention can be lower than P25, and matrix material more is easy to generate electron-hole pair under the condition of UV-irradiation, has higher photocatalytic activity.
Embodiment
Further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
At first adopt sol-gel method to prepare nano composite material titanium dioxide/carbon nanotube, utilize chitosan then, make titanium dioxide/carbon nanotube/chitosan matrix material catalytic film as linking agent.The different mass of carbon nanotube in composite material film than (1%-10%), is optimized experiment, and then with the analog gas of benzene as indoor VOCs, research matrix material rete is to the photocatalytic degradation performance of VOCs.
Embodiment 1 (making processes)
Get the tetrabutyl titanate of 5ml and the dehydrated alcohol of 10ml and place the beaker of 20ml, and stir 30min, obtain water white solution; Other gets carbon nanotube (40-60nm) ultra-sonic dispersion of 0.112g in the dehydrated alcohol of 10ml, ultra-sonic dispersion 15min, obtain homodisperse suspension, then the dehydrated alcohol dispersion liquid of carbon nanotube dropwise is added in the solution of tetrabutyl titanate and stirs, drop rate is 0.5 droplet/second, drip the back and continue violent stirring 30min, obtain even mixed solution.Dropwise be added to the acetic acid solution (mol ratio of acetate and water is 0.055: 1) of 1.5ml in the mixing solutions with syringe then and stir, 0.2 droplet/second of rate of addition, drip the back and continue to stir 30min, obtain the colloidal sol of titanium dioxide/carbon nanotube, drying at room temperature then, ageing 4d, obtain the xerogel of titanium dioxide/carbon nanotube, xerogel is placed 60 ℃ of dry 12h of loft drier, grind with mortar then, obtain powder, powder is placed 450 ℃ of calcinations of retort furnace, intensification is 2.5 ℃/min.Make titanium dioxide/carbon nano tube compound material (mass ratio of carbon nanotube and titanium dioxide is 1: 10).
Chitosan is dissolved in 1% the acetic acid solution, obtain the acetic acid solution of chitosan, mass ratio according to titanium dioxide/carbon nano tube compound material and chitosan is 10: 1 then, titanium oxide/carbon nano tube compound material is added in the acetic acid solution of 10ml chitosan, make the mucus of titanium dioxide/carbon nanotube/chitosan, then mucus is coated with and is plated in the on glass of dried and clean, after the drying at room temperature, after placing 80 ℃ of dry 12h of loft drier, obtain titanium dioxide/carbon nanotube/chitosan matrix material catalytic film.By to the experiment of the photocatalytic degradation of gas-phase benzene, under the irradiation of the UV-light of 365nm, the degraded to benzene behind the 3h reaches 89.6%.
Embodiment 2 (making processes)
Get the tetrabutyl titanate of 5ml and the dehydrated alcohol of 10ml and place the beaker of 20ml, and stir 30min, obtain water white solution; Other gets carbon nanotube (40-60nm) ultra-sonic dispersion of 0.056g in the dehydrated alcohol of 10ml, ultra-sonic dispersion 15min, obtain homodisperse suspension, then the dehydrated alcohol dispersion liquid of carbon nanotube dropwise is added in the solution of tetrabutyl titanate and stirs, drop rate is 0.5 droplet/second, drip the back and continue violent stirring 30min, obtain even mixed solution.Dropwise be added to the acetic acid solution (mol ratio of acetate and water is 0.055: 1) of 1.5ml in the mixing solutions with syringe then and stir, 0.2 droplet/second of rate of addition, drip the back and continue to stir 30min, obtain the colloidal sol of titanium dioxide/carbon nanotube, drying at room temperature then, ageing 4d, obtain the xerogel of titanium dioxide/carbon nanotube, xerogel is placed 60 ℃ of dry 12h of loft drier, grind with mortar then, obtain powder, powder is placed 450 ℃ of calcinations of retort furnace, intensification is 2.5 ℃/min.Make titanium dioxide/carbon nano tube compound material (mass ratio of carbon nanotube and titanium dioxide is 1: 20).
Chitosan is dissolved in 1% the acetic acid solution, obtain the acetic acid solution of chitosan, mass ratio according to titanium dioxide/carbon nano tube compound material and chitosan is 10: 1 then, titanium oxide/carbon nano tube compound material is added in the acetic acid solution of 10ml chitosan, make the mucus of titanium dioxide/carbon nanotube/chitosan, then mucus is coated with and is plated in the on glass of dried and clean, after the drying at room temperature, after placing 80 ℃ of dry 12h of loft drier, obtain titanium dioxide/carbon nanotube/chitosan matrix material catalytic film.By to the experiment of the photocatalytic degradation of gas-phase benzene, under the irradiation of the UV-light of 365nm, the degraded to benzene behind the 3h reaches 88%.
Embodiment 3 (making processes)
Get the tetrabutyl titanate of 5ml and the dehydrated alcohol of 10ml and place the beaker of 20ml, and stir 30min, obtain water white solution; Other gets carbon nanotube (40-60nm) ultra-sonic dispersion of 0.0224g in the dehydrated alcohol of 10ml, ultra-sonic dispersion 15min, obtain homodisperse suspension, then the dehydrated alcohol dispersion liquid of carbon nanotube dropwise is added in the solution of tetrabutyl titanate and stirs, drop rate is 0.5 droplet/second, drip the back and continue violent stirring 30min, obtain even mixed solution.Dropwise be added to the acetic acid solution (mol ratio of acetate and water is 0.055: 1) of 1.5ml in the mixing solutions with syringe then and stir, 0.2 droplet/second of rate of addition, drip the back and continue to stir 30min, obtain the colloidal sol of titanium dioxide/carbon nanotube, drying at room temperature then, ageing 4d, obtain the xerogel of titanium dioxide/carbon nanotube, xerogel is placed 60 ℃ of dry 12h of loft drier, grind with mortar then, obtain powder, powder is placed 450 ℃ of calcinations of retort furnace, intensification is 2.5 ℃/min.Make titanium dioxide/carbon nano tube compound material (mass ratio of carbon nanotube and titanium dioxide is 1: 50).
Chitosan is dissolved in 1% the acetic acid solution, obtain the acetic acid solution of chitosan, mass ratio according to titanium dioxide/carbon nano tube compound material and chitosan is 10: 1 then, titanium oxide/carbon nano tube compound material is added in the acetic acid solution of 10ml chitosan, make the mucus of titanium dioxide/carbon nanotube/chitosan, then mucus is coated with and is plated in the on glass of dried and clean, after the drying at room temperature, after placing 80 ℃ of dry 12h of loft drier, obtain titanium dioxide/carbon nanotube/chitosan matrix material catalytic film.By to the experiment of the photocatalytic degradation of gas-phase benzene, under the irradiation of the UV-light of 365nm, the degraded to benzene behind the 3h reaches 90%.
Embodiment 4 (making processes)
Get the tetrabutyl titanate of 5ml and the dehydrated alcohol of 10ml and place the beaker of 20ml, and stir 30min, obtain water white solution; Other gets carbon nanotube (40-60nm) ultra-sonic dispersion of 0.0112g in the dehydrated alcohol of 10ml, ultra-sonic dispersion 15min, obtain homodisperse suspension, then the dehydrated alcohol dispersion liquid of carbon nanotube dropwise is added in the solution of tetrabutyl titanate and stirs, drop rate is 0.5 droplet/second, drip the back and continue violent stirring 30min, obtain even mixed solution.Dropwise be added to the acetic acid solution (mol ratio of acetate and water is 0.055: 1) of 1.5ml in the mixing solutions with syringe then and stir, 0.2 droplet/second of rate of addition, drip the back and continue to stir 30min, obtain the colloidal sol of titanium dioxide/carbon nanotube, drying at room temperature then, ageing 4d, obtain the xerogel of titanium dioxide/carbon nanotube, xerogel is placed 60 ℃ of dry 12h of loft drier, grind with mortar then, obtain powder, powder is placed 450 ℃ of calcinations of retort furnace, intensification is 2.5 ℃/min.Make titanium dioxide/carbon nano tube compound material (mass ratio of carbon nanotube and titanium dioxide is 1: 100).
Chitosan is dissolved in 1% the acetic acid solution, obtain the acetic acid solution of chitosan, mass ratio according to titanium dioxide/carbon nano tube compound material and chitosan is 10: 1 then, titanium oxide/carbon nano tube compound material is added in the acetic acid solution of 10ml chitosan, make the mucus of titanium dioxide/carbon nanotube/chitosan, then mucus is coated with and is plated in the on glass of dried and clean, after the drying at room temperature, after placing 80 ℃ of dry 12h of loft drier, obtain titanium dioxide/carbon nanotube/chitosan matrix material catalytic film.By to the experiment of the photocatalytic degradation of gas-phase benzene, under the irradiation of the UV-light of 365nm, the degraded to benzene behind the 3h reaches 85%.
Comparative Examples (making processes)
Utilize commercial P25 titanium dioxide as photocatalyst, adopt the method for dipping coating to obtain the catalysis rete, the rete of preparation is inhomogeneous, and a little less than the bonding force of carrier, then gas-phase benzene is carried out the photocatalytic degradation experiment, under the irradiation of the UV-light of 365nm, the degradation rate to benzene behind the 3h is 56%, and the matrix material catalysis rete of the titanium dioxide/carbon nanotube/chitosan by comparative descriptions the present invention preparation has good photodegradation to organism.
Claims (3)
1. preparation method with laminated film of photocatalytic-oxidation voltinism, it is characterized in that: the mass ratio 1: 10 of pressing chitosan and carbon nano-tube/titanic oxide composite granule, the carbon nano-tube/titanic oxide composite granule is added in the 1wt% acetic acid solution of 10ml chitosan, and stir, obtain mucus; Then mucus is coated with and is plated on the carrier, 80 ℃ of dryings are 1 day in 4 hours rearmounted loft drier of drying at room temperature, eliminate residual moisture and acetate, promptly get described laminated film.
2. preparation method according to claim 1 is characterized in that: the preparation process of described carbon nano-tube/titanic oxide composite granule is as follows:
1) gets the tetrabutyl titanate of 5ml and the dehydrated alcohol of 10ml and place the beaker of 20ml, and stir 30min, obtain water white solution; In the dehydrated alcohol of 10ml, ultra-sonic dispersion 15min obtains homodisperse suspension with the carbon nanotube ultra-sonic dispersion of 0.0112-0.112g 40-60nm;
2) the dehydrated alcohol dispersion liquid of the carbon nanotube that step 1) is obtained dropwise is added in the ethanol solution of the tetrabutyl titanate that step 1) obtains and stirs, and drop rate is 0.5 droplet/second, drips the back and continues violent stirring 30min, obtains even mixed solution;
3) with syringe the acetic acid solution of 1.5ml dropwise being added to step 2 then) in the mixing solutions that obtains and stir, the mol ratio of acetate and water is 0.055: 1; 0.2 droplet/second of rate of addition drips the back and continue to stir 30min, obtains the colloidal sol of titanium dioxide/carbon nanotube, drying at room temperature then, and ageing 4d obtains the xerogel of titanium dioxide/carbon nanotube;
4) xerogel is placed 60 ℃ of dry 12h of loft drier, grind to powder with mortar then, again powder is placed 450 ℃ of calcinations of retort furnace, heat up, make titanium dioxide/carbon nano-tube composite powder to 2-3 ℃/min.
3. the laminated film with photocatalytic-oxidation voltinism is characterized in that, described laminated film is prepared by the described method of claim 1.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972641A (en) * | 2010-10-13 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area titanium dioxide nanotube film as well as preparation method and application thereof |
| CN102240561A (en) * | 2011-05-06 | 2011-11-16 | 华北电力大学 | Preparation method of CS/TiO2-NTs composite photocatalyst |
| CN105806923A (en) * | 2016-03-18 | 2016-07-27 | 陕西师范大学 | Preparation method and application of carbon nanotube/ titanium dioxide/carboxymethyl chitosan nanometer composite electrochemical sensing material |
| CN108786727A (en) * | 2018-05-31 | 2018-11-13 | 安徽科浦环保科技有限公司 | A kind of preparation method for the composite activated carbon fibre except formaldehyde |
| CN109080359A (en) * | 2018-08-17 | 2018-12-25 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of the ageing-resistant transfer membrane of stretch-proof |
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| CN1827225A (en) * | 2006-04-07 | 2006-09-06 | 南京工业大学 | Method for preparing TiO2 photocatalytic film doped with non-metallic element |
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| CN1827225A (en) * | 2006-04-07 | 2006-09-06 | 南京工业大学 | Method for preparing TiO2 photocatalytic film doped with non-metallic element |
| WO2008000045A1 (en) * | 2006-06-30 | 2008-01-03 | University Of Wollongong | Nanostructured composites |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972641A (en) * | 2010-10-13 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area titanium dioxide nanotube film as well as preparation method and application thereof |
| CN101972641B (en) * | 2010-10-13 | 2012-05-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area titanium dioxide nanotube film as well as preparation method and application thereof |
| CN102240561A (en) * | 2011-05-06 | 2011-11-16 | 华北电力大学 | Preparation method of CS/TiO2-NTs composite photocatalyst |
| CN105806923A (en) * | 2016-03-18 | 2016-07-27 | 陕西师范大学 | Preparation method and application of carbon nanotube/ titanium dioxide/carboxymethyl chitosan nanometer composite electrochemical sensing material |
| CN108786727A (en) * | 2018-05-31 | 2018-11-13 | 安徽科浦环保科技有限公司 | A kind of preparation method for the composite activated carbon fibre except formaldehyde |
| CN109080359A (en) * | 2018-08-17 | 2018-12-25 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of the ageing-resistant transfer membrane of stretch-proof |
| CN111268639A (en) * | 2020-02-19 | 2020-06-12 | 东华大学 | Multi-stimulus response actuating film and preparation and application thereof |
| CN111268639B (en) * | 2020-02-19 | 2023-08-18 | 东华大学 | Multi-stimulus response actuation film and preparation and application thereof |
| CN111389365A (en) * | 2020-04-16 | 2020-07-10 | 郑州大学 | Carbon nanotube/titanium dioxide composite film and preparation method and application thereof |
| CN114149716A (en) * | 2021-12-31 | 2022-03-08 | 广东美涂士建材股份有限公司 | Environment-friendly formaldehyde-resistant acid-alkali-resistant industrial coating |
| CN114292495A (en) * | 2022-01-10 | 2022-04-08 | 深圳市佳迪达新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
| CN114292495B (en) * | 2022-01-10 | 2022-08-19 | 深圳市佳迪达新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
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