CN109331805B - Preparation method of carbon fiber loaded nano titanium dioxide photocatalytic composite material - Google Patents
Preparation method of carbon fiber loaded nano titanium dioxide photocatalytic composite material Download PDFInfo
- Publication number
- CN109331805B CN109331805B CN201811361011.7A CN201811361011A CN109331805B CN 109331805 B CN109331805 B CN 109331805B CN 201811361011 A CN201811361011 A CN 201811361011A CN 109331805 B CN109331805 B CN 109331805B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- titanium dioxide
- nano titanium
- coupling agent
- silane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 50
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 4
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 claims description 3
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 claims description 3
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 230000000977 initiatory effect Effects 0.000 abstract 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a preparation method of a carbon fiber loaded nano titanium dioxide photocatalytic composite material, which comprises the following steps: (1) performing surface treatment on the carbon fiber by using hydrogen peroxide to obtain oxidized carbon fiber; (2) carrying out oxidation treatment on the carbon fiber to react with a coupling agent containing vinyl silane to obtain a coupling agent modified carbon fiber containing vinyl silane; (3) reacting the nano titanium dioxide with a coupling agent containing vinyl silane to obtain vinyl silane coupling agent modified nano titanium dioxide; (4) mixing the carbon fiber modified by the coupling agent containing vinyl silane, the nano titanium dioxide modified by the coupling agent containing vinyl silane and a dimercapto compound, and initiating the reaction between mercapto and vinyl by using ultraviolet light to finally obtain the carbon fiber loaded nano titanium dioxide photocatalytic composite material. The invention has the advantages of short reaction period, high yield, less by-products and harmlessness, and the obtained photocatalytic composite material has high photocatalytic activity.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method of a carbon fiber loaded nano titanium dioxide photocatalytic composite material.
Background
Since the 21 st century, the pace of industrialization has been accelerated in China, and with this, more and more resources and environmental problems need to be dealt with. The nano titanium dioxide is a photocatalytic material with excellent performance, has the advantages of high activity, low cost, environmental friendliness and the like, and is widely applied to treatment of various environmental pollutions. However, the powdery nano titanium dioxide has the problems of easy inactivation, easy agglomeration, difficult separation and recovery and the like, which is one of the important reasons for limiting the large-scale application of the nano titanium dioxide in the practical production. The important approach for solving the problem is to load the nano titanium dioxide on a proper carrier, and the current commonly used carriers comprise carbon fibers, carbon nanotubes, activated carbon and the like. Compared with other carriers, the carbon fiber has larger specific surface area and strong response to visible light, greatly improves the photocatalytic activity and stability of the nano titanium dioxide, and is an ideal carrier for loading the nano titanium dioxide. Therefore, the photocatalytic composite material prepared by loading the nano titanium dioxide on the carbon fiber has wide application in the fields of environmental pollution and life production.
Disclosure of Invention
The invention aims to solve the problems that: the preparation method of the carbon fiber loaded nano titanium dioxide photocatalytic composite material is short in reaction period, high in yield, few in by-products and harmless, and the obtained photocatalytic composite material is high in photocatalytic activity.
The technical scheme provided by the invention for solving the problems is as follows: a preparation method of a carbon fiber loaded nano titanium dioxide photocatalytic composite material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: immersing 5g of carbon fiber into 100-200 mL of hydrogen peroxide with the mass percent solubility of 30%, performing ultrasonic treatment for 30-60 minutes at room temperature, then reacting for 1-3 hours under the condition of oil bath at 60-90 ℃, cleaning the product for 5 times by using deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 110 ℃ to obtain the oxidation-treated carbon fiber;
step two: adding 5g of oxidized carbon fiber into 100-200 mL of mixed solution of ethanol and a coupling agent containing vinyl silane, wherein the volume ratio of the ethanol to the coupling agent containing vinyl silane is 97:3, adjusting the pH value of the solution to 4-6 with acetic acid, performing ultrasonic treatment for 30-60 minutes at room temperature, then reacting for 4-8 hours under the condition of oil bath at 60-90 ℃, cleaning a product for 5 times with the mixed solution of ethanol and deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 100 ℃ to obtain the carbon fiber modified with the coupling agent containing vinyl silane;
step three: dispersing 1g of nano titanium dioxide into 30-50 mL of a mixed solution of ethanol and a coupling agent containing vinyl silane in a volume ratio of 97:3, adjusting the pH value of the solution to 4-6 with acetic acid, performing ultrasonic treatment for 30-60 minutes at room temperature, then reacting for 4-6 hours under the condition of oil bath at 60-80 ℃, cleaning a product for 5 times with the mixed solution of ethanol and deionized water after the reaction is finished, and then drying for 24 hours in a vacuum drying oven at 120 ℃ to obtain the nano titanium dioxide modified by the coupling agent containing vinyl silane;
step four: uniformly dispersing 2g of carbon fiber modified by a vinyl silane-containing coupling agent, 0.5g of nano titanium dioxide modified by a vinyl silane-containing coupling agent and 0.1-1 g of dimercapto compound in 80-150 mL of dimethylformamide, performing ultrasonic treatment for 30-60 minutes at room temperature, adding 0.01-0.1 g of photoinitiator, irradiating for 10-30 minutes by adopting ultraviolet light with the wavelength of 365nm, performing suction filtration after the reaction is finished, cleaning for 4 times by using dimethylformamide, and drying for 48 hours in a vacuum drying oven at 110 ℃ to obtain the carbon fiber loaded nano titanium dioxide photocatalytic composite material.
Preferably, the coupling agent containing vinyl silane in the second step is any one of vinyl trimethoxy silane, vinyl triethoxy silane, methyl vinyl diethoxy silane, vinyl triisopropoxy silane, methacryloxypropyl trimethoxy silane and methacryloxypropyl triethoxy silane.
Preferably, the dimercapto compound of step four is any one of 1, 4-butanedithiol, 1, 6-hexanedithiol, 1, 3-propanedithiol or 1, 5-pentanethiol.
Preferably, the photoinitiator in the fourth step is any one of benzophenone, benzoin n-butyl ether, benzoin dimethyl ether or 1-hydroxycyclohexyl phenyl ketone.
Compared with the prior art, the invention has the advantages that: according to the invention, the nano titanium dioxide is loaded on the surface of the carbon fiber by adopting a click chemistry method, the reaction period is shorter, the yield is high, the byproducts are less and harmless, and the obtained photocatalytic composite material has high photocatalytic activity. The carbon fiber loaded nano titanium dioxide is adopted, so that organic pollutants can be effectively degraded, the problems that a carbonaceous material is easy to reach adsorption saturation, powdery titanium dioxide is easy to recover and the like are solved, meanwhile, the specific surface area of the material can be increased, the electronic interface effect is enhanced, and the stability of the material is increased; meanwhile, the invention solves the problems of weak selective adsorption capacity of the nano titanium dioxide, easy secondary agglomeration in the solution and the like, and the stability of the nano titanium dioxide can be improved by loading the nano titanium dioxide on the carbon fiber; in addition, the carbon fiber and the nano titanium dioxide have good synergistic effect, so that the efficiency of the photocatalyst can be effectively improved, and the application of the nano titanium dioxide in the field of photocatalysis is expanded.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, so that how to implement the technical means for solving the technical problems and achieving the technical effects of the present invention can be fully understood and implemented.
Example 1:
this example illustrates a method for preparing a carbon fiber-supported nano titanium dioxide photocatalytic composite material according to the present invention.
The first step is as follows: immersing 5g of carbon fiber into 100mL of hydrogen peroxide with the mass percent solubility of 30%, performing ultrasonic treatment for 30 minutes at room temperature, then reacting for 3 hours under the condition of oil bath at 60 ℃, cleaning the product for 5 times by using deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 110 ℃ to obtain the oxidation-treated carbon fiber;
the second step is that: adding 5g of oxidation-treated carbon fiber into 100mL of ethanol and vinyl trimethoxy silane mixed solution with the volume ratio of 97:3, adjusting the pH value of the solution to 6 by using acetic acid, carrying out ultrasonic treatment for 30 minutes at room temperature, then reacting for 8 hours under the condition of oil bath at 60 ℃, cleaning a product for 5 times by using ethanol and deionized water mixed solution after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 100 ℃ to obtain the vinyl silane coupling agent-containing modified carbon fiber;
the third step: dispersing 1g of nano titanium dioxide into 30mL of a mixed solution of ethanol and vinyl trimethoxy silane with a volume ratio of 97:3, adjusting the pH value of the solution to 6 by using acetic acid, carrying out ultrasonic treatment for 30 minutes at room temperature, then reacting for 6 hours under the condition of oil bath at 60 ℃, cleaning a product for 5 times by using a mixed solution of ethanol and deionized water after the reaction is finished, and then drying for 24 hours in a vacuum drying oven at 120 ℃ to obtain the vinyl silane-containing coupling agent modified nano titanium dioxide;
the fourth step: uniformly dispersing 2g of carbon fiber modified by a vinyl silane-containing coupling agent, 0.5g of nano titanium dioxide modified by a vinyl silane-containing coupling agent and 0.1g of 1, 4-butanedithiol in 80mL of dimethylformamide, carrying out ultrasonic treatment at room temperature for 30 minutes, then adding 0.01g of benzophenone, irradiating for 30 minutes by adopting ultraviolet light with the wavelength of 365nm, carrying out suction filtration after the reaction is finished, cleaning for 4 times by using dimethylformamide, and drying in a vacuum drying oven at 110 ℃ for 48 hours to obtain the carbon fiber loaded nano titanium dioxide photocatalytic composite material.
Example 2:
this example illustrates a method for preparing a carbon fiber-supported nano titanium dioxide photocatalytic composite material according to the present invention.
The first step is as follows: soaking 5g of carbon fiber into 150mL of hydrogen peroxide with the mass percent solubility of 30%, performing ultrasonic treatment for 45 minutes at room temperature, then reacting for 2 hours under the condition of an oil bath at 80 ℃, cleaning a product for 5 times by using deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 110 ℃ to obtain oxidized carbon fiber;
the second step is that: adding 5g of oxidation-treated carbon fiber into 150mL of mixed solution of ethanol and methacryloxypropyltrimethoxysilane with the volume ratio of 97:3, adjusting the pH value of the solution to 5 with acetic acid, carrying out ultrasonic treatment for 45 minutes at room temperature, then reacting for 6 hours under the condition of an oil bath at 80 ℃, cleaning a product for 5 times with the mixed solution of ethanol and deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 100 ℃ to obtain the vinyl-containing silane coupling agent modified carbon fiber;
the third step: dispersing 1g of nano titanium dioxide into 40mL of mixed solution of ethanol and methacryloxypropyltrimethoxysilane, wherein the volume ratio of the ethanol to the methacryloxypropyltrimethoxysilane is 97:3, adjusting the pH value of the solution to 5 with acetic acid, carrying out ultrasonic treatment for 45 minutes at room temperature, then reacting for 5 hours under the condition of 70 ℃ oil bath, cleaning a product after the reaction for 5 times with mixed solution of ethanol and deionized water, and then drying for 24 hours in a 120 ℃ vacuum drying oven to obtain vinyl-containing silane coupling agent modified nano titanium dioxide;
the fourth step: uniformly dispersing 2g of carbon fiber modified by a vinyl silane-containing coupling agent, 0.5g of nano titanium dioxide modified by a vinyl silane-containing coupling agent and 0.8g of 1, 6-hexanedithiol in 100mL of dimethylformamide, performing ultrasonic treatment for 45 minutes at room temperature, adding 0.08g of benzoin n-butyl ether, irradiating for 20 minutes by using ultraviolet light with the wavelength of 365nm, performing suction filtration after the reaction is finished, cleaning for 4 times by using the dimethylformamide, and drying for 48 hours in a vacuum drying oven at 110 ℃ to obtain the carbon fiber loaded nano titanium dioxide photocatalytic composite material.
Example 3:
this example illustrates a method for preparing a carbon fiber-supported nano titanium dioxide photocatalytic composite material according to the present invention.
The first step is as follows: immersing 5g of carbon fiber into 200mL of hydrogen peroxide with the mass percent solubility of 30%, performing ultrasonic treatment for 60 minutes at room temperature, then reacting for 1 hour under the condition of oil bath at 90 ℃, cleaning a product for 5 times by using deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 110 ℃ to obtain the oxidation-treated carbon fiber;
the second step is that: adding 5g of oxidation-treated carbon fiber into 200mL of mixed solution of ethanol and methyl vinyl diethoxysilane with the volume ratio of 97:3, adjusting the pH value of the solution to 4 by using acetic acid, carrying out ultrasonic treatment for 60 minutes at room temperature, then reacting for 4 hours under the condition of oil bath at 90 ℃, cleaning the product for 5 times by using the mixed solution of ethanol and deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 100 ℃ to obtain the vinyl silane-containing coupling agent modified carbon fiber;
the third step: dispersing 1g of nano titanium dioxide into 50mL of mixed solution of ethanol and methyl vinyl diethoxysilane with the volume ratio of 97:3, adjusting the pH value of the solution to 4 by using acetic acid, carrying out ultrasonic treatment for 60 minutes at room temperature, then reacting for 4 hours under the condition of 80 ℃ oil bath, cleaning the product for 5 times by using the mixed solution of ethanol and deionized water after the reaction is finished, and then drying for 24 hours in a 120 ℃ vacuum drying oven to obtain the vinyl silane-containing coupling agent modified nano titanium dioxide;
the fourth step: uniformly dispersing 2g of carbon fiber modified by a vinyl silane-containing coupling agent, 0.5g of nano titanium dioxide modified by a vinyl silane-containing coupling agent and 1g of 1, 5-pentanethiol in 150mL of dimethylformamide, carrying out ultrasonic treatment at room temperature for 60 minutes, then adding 0.1g of benzoin dimethyl ether, irradiating for 10 minutes by adopting ultraviolet light with the wavelength of 365nm, carrying out suction filtration after the reaction is finished, washing for 4 times by using the dimethylformamide, and drying for 48 hours in a vacuum drying oven at 110 ℃ to obtain the carbon fiber loaded nano titanium dioxide photocatalytic composite material.
The invention has the beneficial effects that: according to the invention, the nano titanium dioxide is loaded on the surface of the carbon fiber by adopting a click chemistry method, the reaction period is shorter, the yield is high, the byproducts are less and harmless, and the obtained photocatalytic composite material has high photocatalytic activity. The carbon fiber loaded nano titanium dioxide is adopted, so that organic pollutants can be effectively degraded, the problems that a carbonaceous material is easy to reach adsorption saturation, powdery titanium dioxide is easy to recover and the like are solved, meanwhile, the specific surface area of the material can be increased, the electronic interface effect is enhanced, and the stability of the material is increased; meanwhile, the invention solves the problems of weak selective adsorption capacity of the nano titanium dioxide, easy secondary agglomeration in the solution and the like, and the stability of the nano titanium dioxide can be improved by loading the nano titanium dioxide on the carbon fiber; in addition, the carbon fiber and the nano titanium dioxide have good synergistic effect, so that the efficiency of the photocatalyst can be effectively improved, and the application of the nano titanium dioxide in the field of photocatalysis is expanded.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (4)
1. A preparation method of a carbon fiber loaded nano titanium dioxide photocatalytic composite material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: immersing 5g of carbon fiber into 100-200 mL of hydrogen peroxide with the mass percent solubility of 30%, performing ultrasonic treatment for 30-60 minutes at room temperature, then reacting for 1-3 hours under the condition of oil bath at 60-90 ℃, cleaning the product for 5 times by using deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 110 ℃ to obtain the oxidation-treated carbon fiber;
step two: adding 5g of oxidized carbon fiber into 100-200 mL of mixed solution of ethanol and a coupling agent containing vinyl silane, wherein the volume ratio of the ethanol to the coupling agent containing vinyl silane is 97:3, adjusting the pH value of the solution to 4-6 with acetic acid, performing ultrasonic treatment for 30-60 minutes at room temperature, then reacting for 4-8 hours under the condition of oil bath at 60-90 ℃, cleaning a product for 5 times with the mixed solution of ethanol and deionized water after the reaction is finished, and drying for 24 hours in a vacuum drying oven at 100 ℃ to obtain the carbon fiber modified with the coupling agent containing vinyl silane;
step three: dispersing 1g of nano titanium dioxide into 30-50 mL of a mixed solution of ethanol and a coupling agent containing vinyl silane in a volume ratio of 97:3, adjusting the pH value of the solution to 4-6 with acetic acid, performing ultrasonic treatment for 30-60 minutes at room temperature, then reacting for 4-6 hours under the condition of oil bath at 60-80 ℃, cleaning a product for 5 times with the mixed solution of ethanol and deionized water after the reaction is finished, and then drying for 24 hours in a vacuum drying oven at 120 ℃ to obtain the nano titanium dioxide modified by the coupling agent containing vinyl silane;
step four: uniformly dispersing 2g of carbon fiber modified by a vinyl silane-containing coupling agent, 0.5g of nano titanium dioxide modified by a vinyl silane-containing coupling agent and 0.1-1 g of dimercapto compound in 80-150 mL of dimethylformamide, performing ultrasonic treatment for 30-60 minutes at room temperature, adding 0.01-0.1 g of photoinitiator, irradiating for 10-30 minutes by adopting ultraviolet light with the wavelength of 365nm, performing suction filtration after the reaction is finished, cleaning for 4 times by using dimethylformamide, and drying for 48 hours in a vacuum drying oven at 110 ℃ to obtain the carbon fiber loaded nano titanium dioxide photocatalytic composite material.
2. The preparation method of the carbon fiber-supported nano titanium dioxide photocatalytic composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the coupling agent containing vinyl silane in the second step is any one of vinyl trimethoxy silane, vinyl triethoxy silane, methyl vinyl diethoxy silane, vinyl triisopropoxy silane, methacryloxypropyl trimethoxy silane and methacryloxypropyl triethoxy silane.
3. The preparation method of the carbon fiber-supported nano titanium dioxide photocatalytic composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the dimercapto compound in the fourth step is any one of 1, 4-butanedithiol, 1, 6-hexanedithiol, 1, 3-propanedithiol or 1, 5-pentanethiol.
4. The preparation method of the carbon fiber-supported nano titanium dioxide photocatalytic composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the photoinitiator in the fourth step is any one of benzophenone, benzoin n-butyl ether, benzoin dimethyl ether or 1-hydroxycyclohexyl phenyl ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811361011.7A CN109331805B (en) | 2018-11-15 | 2018-11-15 | Preparation method of carbon fiber loaded nano titanium dioxide photocatalytic composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811361011.7A CN109331805B (en) | 2018-11-15 | 2018-11-15 | Preparation method of carbon fiber loaded nano titanium dioxide photocatalytic composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109331805A CN109331805A (en) | 2019-02-15 |
| CN109331805B true CN109331805B (en) | 2021-06-15 |
Family
ID=65315742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811361011.7A Active CN109331805B (en) | 2018-11-15 | 2018-11-15 | Preparation method of carbon fiber loaded nano titanium dioxide photocatalytic composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109331805B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747639B (en) * | 2019-09-09 | 2021-08-31 | 东华大学 | Preparation method of photocatalyst-loaded fabric based on covalent bond combination |
| CN112358751A (en) * | 2020-11-25 | 2021-02-12 | 山东益丰生化环保股份有限公司 | mercaptan/alkene-TiO for coating2Method for preparing composite material |
| CN112973437B (en) * | 2021-02-20 | 2022-08-26 | 武汉绿知行环保科技有限公司 | Formaldehyde removal master batch for air purification device and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031022A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for modifying nano titanium dioxide sol by utilizing silane coupling agent |
| CN105268400A (en) * | 2015-09-30 | 2016-01-27 | 江苏苏通碳纤维有限公司 | Method for supporting nanometer titanium dioxide on active carbon fibers |
| CN105646945A (en) * | 2016-03-30 | 2016-06-08 | 南昌航空大学 | Method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by aid of mercapto-alkene click reaction |
| CN105778153A (en) * | 2016-03-30 | 2016-07-20 | 南昌航空大学 | Preparation method of polyhedral oligomeric silsesquioxane-grafted carbon fiber reinforcement |
| CN106268729A (en) * | 2016-08-12 | 2017-01-04 | 青海荷洁纳米材料科技有限公司 | A kind of preparation method of carbon fiber loaded photocatalysis material of titanium dioxide |
-
2018
- 2018-11-15 CN CN201811361011.7A patent/CN109331805B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031022A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for modifying nano titanium dioxide sol by utilizing silane coupling agent |
| CN105268400A (en) * | 2015-09-30 | 2016-01-27 | 江苏苏通碳纤维有限公司 | Method for supporting nanometer titanium dioxide on active carbon fibers |
| CN105646945A (en) * | 2016-03-30 | 2016-06-08 | 南昌航空大学 | Method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by aid of mercapto-alkene click reaction |
| CN105778153A (en) * | 2016-03-30 | 2016-07-20 | 南昌航空大学 | Preparation method of polyhedral oligomeric silsesquioxane-grafted carbon fiber reinforcement |
| CN106268729A (en) * | 2016-08-12 | 2017-01-04 | 青海荷洁纳米材料科技有限公司 | A kind of preparation method of carbon fiber loaded photocatalysis material of titanium dioxide |
Non-Patent Citations (2)
| Title |
|---|
| Photocatalytic Oxidation of Arsenite by a Composite of Titanium Dioxide and Activated Carbon Fiber;Shuhua Yao et al.;《Photochemistry and Photobiology》;20101231;第86卷;第1215-1221页 * |
| 活性碳纤维负载纳米二氧化钛对气相中丙酮的光催化降解;王得泰等;《化学与生物工程》;20071231;第24卷(第11期);摘要、第1.2部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109331805A (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109331805B (en) | Preparation method of carbon fiber loaded nano titanium dioxide photocatalytic composite material | |
| JP7011350B2 (en) | A method for producing nanocrystals of graphene-based hollow cobalt sulfide that can efficiently activate persulfate. | |
| CN108855083B (en) | Method for removing sulfonamides in water by activating peracetic acid with modified zeolite | |
| CN109465017B (en) | Controllable preparation method and application of heptacopper tetrasulfide-nonacopper octasulfide heterostructure hollow cubic catalyst | |
| CN107252696B (en) | A kind of preparation method of sisal hemp carbon fiber photochemical catalyst | |
| CN103537313A (en) | Catalyst for benzene hydroxylation-based phenol preparation and preparation method thereof | |
| JP2014504252A (en) | Manufacturing method and application of manganese dioxide nanorods | |
| CN102407147A (en) | Preparation method and application of ZnIn2S4-graphene composited photochemical catalyst | |
| CN103480399A (en) | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof | |
| CN112536049B (en) | Bi (Bi) 2 Se 3 And TiO 2 Nanocomposite material, preparation method and application thereof | |
| CN104607228A (en) | Preparation method for alpha-Fe2O3 quantum dot/nitrogen-doped graphene composite material | |
| CN109046450B (en) | BiOCl/(BiO)2CO3Preparation method and application of loaded cellulose acetate/fibroin hybrid membrane | |
| CN110860283A (en) | Preparation method for synthesizing carbon fiber-bismuth vanadate photocatalytic material by hydrothermal method | |
| CN110404544A (en) | A kind of bimetallic catalytic material and its preparation method and application method | |
| CN112718009A (en) | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof | |
| CN105251483B (en) | A kind of controllable preparation Ag modifies TiO2The method of nano flower photochemical catalyst | |
| CN109433237A (en) | A kind of TiO2-Ti3C2-CoSxNanocrystal photochemical catalyst and preparation method thereof | |
| CN102941118A (en) | Au nanometer core-shell structure catalyst and preparation method thereof | |
| CN105013500A (en) | Heterogeneous Fenton catalyst for degrading azo dye wastewater as well as preparation method and application of heterogeneous Fenton catalyst | |
| CN111659450A (en) | Ag3PO4/g-C3N4@MoS2Composite photocatalytic material and preparation method and application thereof | |
| CN109046466A (en) | A kind of photochemical catalyst and its preparation method and application that the derivative carbon-based material of ZIF-8 is CdS-loaded | |
| CN104667973A (en) | Catalyst carrier material and preparation method thereof | |
| CN112973744A (en) | Novel photoelectric catalyst and preparation method thereof | |
| CN102728409B (en) | Preparation method of high-catalytic efficiency and recyclable photocatalyst | |
| CN106179295B (en) | A kind of photocatalytic activity Carbon fibe and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221011 Address after: 331200 South side of National Road 105, Zhangshu City, Yichun City, Jiangxi Province (Yanghu Industrial Zone) Patentee after: JIANGXI GUOJI NANO SCIENCE AND TECHNOLOGY CO.,LTD. Address before: No. 696 Fenghe Road, Nanchang, Jiangxi Province, Jiangxi Patentee before: NANCHANG HANGKONG University |