CN108126726B - Flexible large-area Ta3N5Nano-rod array carbon fiber cloth and preparation method thereof - Google Patents
Flexible large-area Ta3N5Nano-rod array carbon fiber cloth and preparation method thereof Download PDFInfo
- Publication number
- CN108126726B CN108126726B CN201711175250.9A CN201711175250A CN108126726B CN 108126726 B CN108126726 B CN 108126726B CN 201711175250 A CN201711175250 A CN 201711175250A CN 108126726 B CN108126726 B CN 108126726B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- fiber cloth
- area
- tantalum
- flexible large
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 79
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 79
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000004744 fabric Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002073 nanorod Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 9
- 238000003491 array Methods 0.000 claims abstract description 6
- 241000894006 Bacteria Species 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 238000005121 nitriding Methods 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000003481 tantalum Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- WUSPVAHLRCJNMG-UHFFFAOYSA-D tantalum(5+) pentasulfate Chemical compound [Ta+5].[Ta+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WUSPVAHLRCJNMG-UHFFFAOYSA-D 0.000 claims description 3
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 3
- PVZMSIQWTGPSHJ-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO PVZMSIQWTGPSHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- KWUQLGUXYUKOKE-UHFFFAOYSA-N propan-2-ol;tantalum Chemical compound [Ta].CC(C)O.CC(C)O.CC(C)O.CC(C)O.CC(C)O KWUQLGUXYUKOKE-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005067 remediation Methods 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of water pollution treatment materials, and discloses flexible large-area Ta3N5A nano-rod array carbon fiber cloth and a preparation method thereof. The carbon fiber cloth is composed of a carbon fiber primary backing with modified surface and Ta3N5A nanorod composition of Ta3N5The nano rods are large-area uniform arrays and are vertically embedded between fiber gaps of the carbon fiber primary backing. The preparation method is simple, is easy for large-scale production and is Ta3N5The photocatalyst provides an effective way for environmental remediation and large-scale application in the photocatalytic hydrogen production industry; the invention has higher adsorption efficiency and photocatalytic activity, can catalyze and degrade pollutants by utilizing visible light, has stable property and easy recovery, has important application value in the fields of environment, energy and the like, can effectively and quickly purify polluted water and kill bacteria, enriches the product market of environment restoration materials in China and promotes the development of the environment protection industry.
Description
Technical Field
The invention relates to the field of water pollution treatment materials, in particular to flexible large-area Ta3N5A nano-rod array carbon fiber cloth and a preparation method thereof.
Background
The photocatalytic technology has important application value in the aspect of environmental management, and the key point of the technology is to develop a proper photocatalyst. The photocatalytic material on the market is mainly TiO2And (3) nano materials. However, TiO2Can only be driven by ultraviolet light (only accounting for 4 percent of the energy of the sunlight) in the sunlight to play a role, and has low utilization rate of the sunlight and unsatisfactory catalytic performance. Therefore, the development of a novel environment-friendly, efficient and wide-spectrum-driven photocatalytic material product is urgently needed.
Ta3N5The energy gap of the solar cell is about 2.1eV, the ultraviolet light and visible light spectrum (about 44% of the solar energy) in the sunlight can be utilized, and the utilization rate of the sunlight is relatively high. But Ta3N5Face two major problems, one of which is Ta3N5The photocatalyst is a narrow-gap semiconductor material, has high probability of recombination of photo-generated electrons and holes, and seriously restricts the photocatalytic activity of the photocatalyst. Second, nano-sized Ta3N5Although the composite material has a large specific surface area, the composite material is not easy to recover after use, so that resource waste and even secondary pollution are caused, and the two problems seriously restrict the practical application of the composite material.
The chinese patent application No. 201510237951.5 discloses a hollow nano-fiber photocatalyst of tantalum compound and a preparation method thereof, which has achieved a certain effect in improving the photocatalytic activity of the catalyst, but because the metal compound fiber is brittle, poor in flexibility and fragile, there are still many difficulties in the application and recovery processes, and it is difficult to realize industrialization.
Chinese patent application No. 201611057541.3 discloses a functional nanocomposite including a brush-shaped flexible fiber carrier and a plurality of functional nanoparticles sandwiched between bristles of the brush fiber. However, the method fixes the nano particles between the fiber burrs through the raw materials with thermal expansion and cold contraction, the nano particles are easy to fall off, the distribution of the nano particles is difficult to ensure to be uniform, and the treatment effect in the practical application process is unstable.
Disclosure of Invention
In order to solve the technical problem, the invention provides a flexible large-area Ta3N5The nanometer rod array carbon fiber cloth is prepared with Ta3N5The nanorod arrays grow uniformly and are vertically embedded between fiber gaps of the carbon fiber base cloth, organic pollutants in a water body are quickly removed and harmful bacteria are killed under the irradiation of sunlight, and the nano-rod array has the characteristics of low cost, high catalytic activity, stable property and easiness in recovery.
The specific technical scheme of the invention is as follows: the carbon fiber cloth is composed of a carbon fiber primary backing with modified surface and Ta3N5A nanorod composition of Ta3N5The nano rods are large-area uniform arrays and are vertically embedded between fiber gaps of the carbon fiber primary backing.
The carbon fiber cloth is used as an excellent carbon material and can be used as a flexible substrate of a photocatalytic material, which is beneficial to a catalyst (such as Ta)3N5) Separating the photo-generated electron holes, thereby improving the photo-catalytic activity of the photo-generated electron holes; on the other hand, the fabric is easy to recycle because of the large-area flexible cloth shape.
The preparation method of the carbon fiber cloth comprises the following steps:
1) pretreating carbon fiber cloth: placing the carbon fiber in an organic solvent mixed solution for ultrasonic cleaning for 0.5-3 h;
2) carbon fiber cloth modification: soaking the cleaned carbon fiber cloth in an oxidation treatment solution for 1-15h, wherein the reaction temperature is 5-95 ℃;
3) cleaning carbon fiber cloth: soaking and cleaning the surface-modified carbon fiber cloth for 2-10h by using ethylene glycol, and then drying;
4) preparing a nanorod growth system: firstly, arranging carbon fibers in ethanol, then adding tantalum salt into the ethanol, then adding ammonium fluoride and polyethylene glycol, and stirring for 1-12 h;
5）Ta3N5and (3) growing the nanorod array: putting the growth system into a reaction kettle, and reacting for 4-20h at the reaction temperature of 150-;
6) cleaning and nitriding: and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol, drying in an oven at 70-90 ℃ for 6-24h, and then placing in a tube furnace for nitriding in an ammonia atmosphere at 700-.
The preparation method makes Ta3N5The nanorod arrays are in full contact with the carbon fiber cloth fibers, are uniformly compounded, form a good heterojunction, promote the rapid transfer of photon-generated electrons, prolong the service life of photon-generated carriers, improve the visible light photocatalytic activity of the photon-generated carriers, are vertically embedded between fiber gaps of the carbon fiber base cloth, are stable in load, are not easy to fall off, are uniformly dispersed, have a large area, and can meet the requirements of actual production and application.
Preferably, in the step 1), the organic solvent mixture is prepared by mixing water, ethanol and acetone in a volume ratio of 1: (1-5): (1-5).
Preferably, the oxidation treatment liquid in step 2) is one or two of concentrated sulfuric acid with a concentration of 98% and concentrated nitric acid with a concentration of 65%.
The carbon fiber cloth mainly depends on the physical action to adsorb pollutants and the like in water, after oxidation treatment, the surface of the carbon fiber cloth can be modified with a plurality of hydroxyl groups and carboxyl groups, the chemical adsorption of the carbon fiber cloth is facilitated, the adsorption rate and the adsorption quantity are increased, generally, the chemical adsorption is not considered when the carbon fiber cloth adsorbs and treats the pollutants, because the carbon fiber cloth treats the pollutants in the water independently, a large amount of adsorption is carried out firstly, then the pollutants are recovered and then are uniformly and intensively desorbed, the chemical adsorption has saturation, and the desorption is relatively difficult, but Ta grows on the carbon fiber cloth in an array manner3N5The nano-rod can utilize sunlight or light to catalyze and degrade pollutants, the probability of contact between the pollutants adsorbed by chemical action and a catalyst is higher, the pollutants can react with the catalyst more easily, the pollutants are desorbed automatically after the reaction is finished, the adsorption sites are released, and other pollutants can be continuously adsorbed and degradedDye molecules.
Preferably, the tantalum salt in the step 4) is one or more of tantalum butoxide, tantalum ethoxide, tantalum pentachloride, tantalum isopropoxide and tantalum sulfate.
Preferably, in the step 4), the concentration of the tantalum salt is 5-20 mg/mL, the concentration of the ammonium fluoride is 0.05-0.3mg/mL, and the concentration of the polyethylene glycol is 10-20 mg/mL.
Preferably, the filling degree of the reaction kettle in the step 5) is 70-90%.
Preferably, the temperature is programmed in the step 5), and the temperature rise rate is 0.2-4 ℃/min.
Preferably, the number of times of alternate washing in the step 6) is 3 to 5.
Preferably, the carbon fiber cloth is used for removing organic pollutants and harmful bacteria in water.
Compared with the prior art, the invention has the beneficial effects that: the preparation method is simple, is easy for large-scale production and is Ta3N5The photocatalyst provides an effective way for environmental remediation and large-scale application in the photocatalytic hydrogen production industry; the invention has higher adsorption efficiency and photocatalytic activity, can catalyze and degrade pollutants by utilizing visible light, has stable property and easy recovery, has important application value in the fields of environment, energy and the like, can effectively and quickly purify polluted water and kill bacteria, enriches the product market of environment restoration materials in China and promotes the development of the environment protection industry.
Drawings
FIG. 1 is a diagram of flexible large area Ta prepared in the present invention3N5Scanning Electron Microscope (SEM) image of the nano-rod array carbon fiber cloth;
FIG. 2 is a diagram of flexible large area Ta prepared in the present invention3N5Scanning Electron Microscope (SEM) image of the nano-rod array carbon fiber cloth;
FIG. 3 is a diagram of flexible large area Ta prepared in the present invention3N5An X-ray diffraction (XRD) pattern of the nanorod array carbon fiber cloth;
FIG. 4 is a diagram of flexible large area Ta prepared in the present invention3N5Nano-rodA graph of rhodamine (Rh.B) photocatalytic degradation of the array carbon fiber cloth under the irradiation of visible light;
FIG. 5 is a diagram of flexible large area Ta prepared in the present invention3N5And (3) a 5-time circulating photocatalytic degradation curve diagram of rhodamine (Rh.B) by the nanorod array carbon fiber cloth under the irradiation of visible light.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Disposing carbon fibers in a water/ethanol/acetone = 1: 5: 5, ultrasonic cleaning for 3 hours in the organic solvent mixed solution; soaking the cleaned carbon fiber cloth in 98% concentrated sulfuric acid for 1h, wherein the reaction temperature is 95 ℃; soaking and cleaning the surface-modified carbon fiber cloth for 10 hours by using ethylene glycol, and then drying; firstly, carbon fibers are arranged in 85mL of ethanol, then 20mg/mL of tantalum pentachloride is added into the ethanol, then 0.05mg/mL of ammonium fluoride and 20mg/mL of polyethylene glycol are added, and stirring treatment is carried out for 12 hours; putting the growth system into a reaction kettle, wherein the filling degree of the reaction kettle is 70%, the heating rate is 4 ℃/min, the reaction temperature is 200 ℃, and the reaction time is 20 hours; and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol for 3 times, drying in a 90 ℃ drying oven for 6 hours, and then placing in a tubular furnace for nitriding in an ammonia atmosphere at 700 ℃ for 15 hours to obtain the required product.
Example 2
Disposing carbon fibers in a water/ethanol/acetone = 1: 1: 1, ultrasonic cleaning for 0.5h in the organic solvent mixed solution; soaking the cleaned carbon fiber cloth in 65% concentrated nitric acid for 15h at the reaction temperature of 50 ℃; soaking and cleaning the surface-modified carbon fiber cloth for 2 hours by using ethylene glycol, and then drying; firstly, arranging carbon fibers in 85mL of ethanol, then adding 5mg/mL of tantalum ethoxide into the ethanol, then adding 0.1mg/mL of ammonium fluoride and 10mg/mL of polyethylene glycol, and stirring for 1 h; putting the growth system into a reaction kettle, wherein the filling degree of the reaction kettle is 90%, the heating rate is 0.2 ℃/min, the reaction temperature is 150 ℃, and the reaction is carried out for 4 hours; and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol for 4 times, drying in a 70 ℃ drying oven for 24 hours, and then placing in a tubular furnace for nitriding in an ammonia atmosphere at 900 ℃ for 3 hours to obtain the required product.
Example 3
Disposing carbon fibers in a water/ethanol/acetone = 1: 3: 2, ultrasonic cleaning for 2 hours in the organic solvent mixed solution; the cleaned carbon fiber cloth is respectively soaked in 98% concentrated sulfuric acid and 65% concentrated nitric acid for 3 hours, and the reaction temperature is 5 ℃; soaking and cleaning the surface-modified carbon fiber cloth for 5 hours by using ethylene glycol, and then drying; firstly, arranging carbon fibers in 85mL of ethanol, then adding 10mg/mL of tantalum sulfate into the ethanol, then adding 0.3mg/mL of ammonium fluoride and 15mg/mL of polyethylene glycol, and stirring for 6 hours; putting the growth system into a reaction kettle, wherein the filling degree of the reaction kettle is 80%, the heating rate is 2 ℃/min, the reaction temperature is 175 ℃, and the reaction is carried out for 10 hours; and (3) alternately cleaning the array growth product for 5 times by using ultrapure water and absolute ethyl alcohol, drying in an oven at the temperature of 80 ℃ for 12 hours, and then placing in a tubular furnace for nitriding in an ammonia atmosphere at the temperature of 800 ℃ for 8 hours to obtain the required product.
Example 4
Disposing carbon fibers in a water/ethanol/acetone = 1: 1: 1, ultrasonic cleaning for 1h in the organic solvent mixed solution; the cleaned carbon fiber cloth is respectively soaked in 65 percent concentrated nitric acid for 3 hours at the reaction temperature of 50 ℃; soaking and cleaning the surface-modified carbon fiber cloth for 3 hours by using ethylene glycol, and then drying; firstly, arranging carbon fibers in 85mL of ethanol, then adding 15mg/mL of tantalum ethoxide into the ethanol, then adding 0.1mg/mL of ammonium fluoride and 15mg/mL of polyethylene glycol, and stirring for 6 hours; putting the growth system into a reaction kettle, wherein the filling degree of the reaction kettle is 85%, the heating rate is 1 ℃/min, the reaction temperature is 160 ℃, and the reaction time is 10 hours; and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol for 4 times, drying in an oven at the temperature of 80 ℃ for 10 hours, and then placing in a tubular furnace for nitriding in an ammonia atmosphere at the temperature of 750 ℃ for 5 hours to obtain the required product.
Flexible Large area Ta prepared in this example3N5The shape of the nano-rod array carbon fiber cloth is Ta3N5The nanorod arrays are uniformly attached to the surface of the carbon cloth. The scanning electron microscope spectrum is shown in figures 1 and 2, and the X-ray diffraction spectrum is shown in figure 3.
This implementationFor example, in a single rhodamine B (Rh.B) degradation test, the photocatalytic reaction is carried out for 60 min, the degradation efficiency reaches 92.3 percent, and as shown in FIG. 4, carbon fiber cloth and Ta which are independent can be seen according to FIG. 43N5In contrast, rhodamine B is loaded with Ta3N5The content of the nano-rod in the carbon fiber cloth system is obviously reduced along with time, and the nano-rod carbon fiber cloth system is proved to have high catalytic activity and good degradation effect.
In the five-cycle rh.b degradation test, the last degradation efficiency reached 84.2%, as shown in fig. 5.
Example 5
Disposing carbon fibers in a water/ethanol/acetone = 1: 1: 1, ultrasonic cleaning for 1h in the organic solvent mixed solution; the cleaned carbon fiber cloth is respectively soaked in 65 percent concentrated nitric acid for 3 hours at the reaction temperature of 50 ℃; soaking and cleaning the surface-modified carbon fiber cloth for 3 hours by using ethylene glycol, and then drying; firstly, arranging carbon fibers in 85mL of ethanol, then adding 5mg/mL of tantalum ethoxide into the ethanol, then adding 0.1mg/mL of ammonium fluoride and 15mg/mL of polyethylene glycol, and stirring for 6 hours; putting the growth system into a reaction kettle, wherein the filling degree of the reaction kettle is 85%, the heating rate is 1 ℃/min, the reaction temperature is 160 ℃, and the reaction time is 10 hours; and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol for 4 times, drying in an oven at the temperature of 80 ℃ for 10 hours, and then placing in a tubular furnace for nitriding in an ammonia atmosphere at the temperature of 750 ℃ for 5 hours to obtain the required product.
In the embodiment, in a single rhodamine B (Rh.B) degradation test, the photocatalytic reaction is carried out for 60 min, the degradation efficiency reaches 65.5%, and in a five-cycle Rh.B degradation test, the last degradation efficiency reaches 51.8%.
Example 6
Disposing carbon fibers in a water/ethanol/acetone = 1: 1: 1, ultrasonic cleaning for 1h in the organic solvent mixed solution; the cleaned carbon fiber cloth is respectively soaked in 65 percent concentrated nitric acid for 3 hours at the reaction temperature of 50 ℃; soaking and cleaning the surface-modified carbon fiber cloth for 3 hours by using ethylene glycol, and then drying; firstly, arranging carbon fibers in 85mL of ethanol, then adding 20mg/mL of tantalum ethoxide into the ethanol, then adding 0.1mg/mL of ammonium fluoride and 15mg/mL of polyethylene glycol, and stirring for 6 hours; putting the growth system into a reaction kettle, wherein the filling degree of the reaction kettle is 85%, the heating rate is 1 ℃/min, the reaction temperature is 160 ℃, and the reaction time is 10 hours; and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol for 4 times, drying in an oven at the temperature of 80 ℃ for 10 hours, and then placing in a tubular furnace for nitriding in an ammonia atmosphere at the temperature of 750 ℃ for 5 hours to obtain the required product.
In the embodiment, in a single rhodamine B (Rh.B) degradation test, the photocatalytic reaction is carried out for 60 min, the degradation efficiency reaches 86.8%, and in a five-cycle Rh.B degradation test, the last degradation efficiency reaches 72.5%.
Example 7
Disposing carbon fibers in a water/ethanol/acetone = 1: 1: 1, ultrasonic cleaning for 1h in the organic solvent mixed solution; the cleaned carbon fiber cloth is respectively soaked in 65 percent concentrated nitric acid for 3 hours at the reaction temperature of 50 ℃; soaking and cleaning the surface-modified carbon fiber cloth for 3 hours by using ethylene glycol, and then drying; firstly, arranging carbon fibers in 85mL of ethanol, then adding 10mg/mL of tantalum ethoxide into the ethanol, then adding 0.1mg/mL of ammonium fluoride and 15mg/mL of polyethylene glycol, and stirring for 6 hours; putting the growth system into a reaction kettle, wherein the filling degree of the reaction kettle is 85%, the heating rate is 1 ℃/min, the reaction temperature is 180 ℃, and the reaction time is 10 hours; and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol for 4 times, drying in an oven at the temperature of 80 ℃ for 10 hours, and then placing in a tubular furnace for nitriding in an ammonia atmosphere at the temperature of 850 ℃ for 5 hours to obtain the required product.
In the test of single degradation of rhodamine B (Rh.B), the degradation efficiency of the embodiment reaches 79.1%, and in the test of five-time cyclic degradation of Rh.B, the degradation efficiency of the last time reaches 67.8%.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. Flexible large-area Ta3N5The nano-rod array carbon fiber cloth is characterized in that the carbon fiber cloth is composed of a carbon fiber base cloth with a modified surface and Ta3N5A nanorod composition of Ta3N5The nano rods are large-area uniform arrays and are vertically embedded between fiber gaps of the carbon fiber primary backing;
the flexible large-area Ta3N5The preparation method of the nanorod array carbon fiber cloth comprises the following steps:
1) pretreating carbon fiber cloth: placing the carbon fiber in an organic solvent mixed solution for ultrasonic cleaning for 0.5-3 h;
2) carbon fiber cloth modification: soaking the cleaned carbon fiber cloth in an oxidation treatment solution for 1-15h, wherein the reaction temperature is 5-95 ℃;
3) cleaning carbon fiber cloth: soaking and cleaning the surface-modified carbon fiber cloth for 2-10h by using ethylene glycol, and then drying;
4) preparing a nanorod growth system: firstly, arranging carbon fibers in ethanol, then adding tantalum salt into the ethanol, then adding ammonium fluoride and polyethylene glycol, and stirring for 1-12 h;
5）Ta3N5and (3) growing the nanorod array: putting the growth system into a reaction kettle, and reacting for 4-20h at the reaction temperature of 150-;
6) cleaning and nitriding: and (3) alternately cleaning the array growth product by using ultrapure water and absolute ethyl alcohol, drying in an oven at 70-90 ℃ for 6-24h, and then placing in a tube furnace for nitriding in an ammonia atmosphere at 700-.
2. Flexible large area Ta as claimed in claim 13N5The nanorod array carbon fiber cloth is characterized in that in the step 1), the volume ratio of organic solvent mixed liquor, namely water, ethanol and acetone is 1: (1-5): (1-5).
3. The flexible of claim 1Large area Ta3N5The nanorod array carbon fiber cloth is characterized in that the oxidation treatment liquid in the step 2) is one or two of concentrated sulfuric acid with the concentration of 98% and concentrated nitric acid with the concentration of 65%.
4. Flexible large area Ta as claimed in claim 13N5The nanorod array carbon fiber cloth is characterized in that the tantalum salt in the step 4) is one or more of tantalum butoxide, tantalum ethoxide, tantalum pentachloride, tantalum isopropoxide and tantalum sulfate.
5. Flexible large area Ta as claimed in claim 1 or 43N5The nanorod array carbon fiber cloth is characterized in that in the step 4), the concentration of tantalum salt is 5-20 mg/mL, the concentration of ammonium fluoride is 0.05-0.3mg/mL, and the concentration of polyethylene glycol is 10-20 mg/mL.
6. Flexible large area Ta as claimed in claim 13N5The nanorod array carbon fiber cloth is characterized in that the filling degree of the reaction kettle in the step 5) is 70-90%.
7. Flexible large area Ta as claimed in claim 1 or 63N5The nanorod array carbon fiber cloth is characterized in that temperature programming is needed in the step 5), and the temperature rising rate is 0.2-4 ℃/min.
8. Flexible large area Ta as claimed in claim 13N5The nanorod array carbon fiber cloth is characterized in that the number of alternate cleaning times in the step 6) is 3-5.
9. Flexible large area Ta as claimed in claim 13N5The nanorod array carbon fiber cloth is characterized in that the carbon fiber cloth is used for removing organic pollutants and harmful bacteria in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711175250.9A CN108126726B (en) | 2017-11-22 | 2017-11-22 | Flexible large-area Ta3N5Nano-rod array carbon fiber cloth and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711175250.9A CN108126726B (en) | 2017-11-22 | 2017-11-22 | Flexible large-area Ta3N5Nano-rod array carbon fiber cloth and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108126726A CN108126726A (en) | 2018-06-08 |
| CN108126726B true CN108126726B (en) | 2020-08-18 |
Family
ID=62389740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711175250.9A Active CN108126726B (en) | 2017-11-22 | 2017-11-22 | Flexible large-area Ta3N5Nano-rod array carbon fiber cloth and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108126726B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103352211A (en) * | 2013-06-09 | 2013-10-16 | 北京科技大学 | Preparation method of low-dimensional tantalum-based nano-array photo-electrode |
| CN104888833A (en) * | 2015-05-15 | 2015-09-09 | 浙江海洋学院 | Ta3N5/C composite fiber photocatalyst and preparation method thereof |
-
2017
- 2017-11-22 CN CN201711175250.9A patent/CN108126726B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103352211A (en) * | 2013-06-09 | 2013-10-16 | 北京科技大学 | Preparation method of low-dimensional tantalum-based nano-array photo-electrode |
| CN104888833A (en) * | 2015-05-15 | 2015-09-09 | 浙江海洋学院 | Ta3N5/C composite fiber photocatalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Hot-Electrons Mediated Efficient Visible-Light Photocatalysis of Hierarchical Black Au-TiO2 Nanorod Arrays on Flexible Substrate;Huimin Shi等;《Adv. Mater. Interfaces》;20160916;第3卷;文献号1600588 * |
| Vertically Aligned Ta3N5 Nanorod Arrays for Solar-Driven Photoelectrochemical Water Splitting;Yanbo Li等;《Adv. Mater.》;20120918;第25卷;125-131 * |
| 铌、钽基光催化材料的水热合成及其光催化性能探究;邬晶晶;《中国期刊网全文数据库 工程科技I辑》;20150615;57、61 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108126726A (en) | 2018-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11111605B2 (en) | Iodine doped bismuthyl carbonate nanosheet and molybdenum disulfide modified carbon nanofiber composites, preparation method and application thereof | |
| CN108772108B (en) | Visible light response titanium dioxide nanowire/metal organic framework/carbon nanofiber membrane and preparation method and application thereof | |
| CN108940338B (en) | Potassium-doped porous carbon nitride photocatalyst and preparation method and application thereof | |
| CN112516964B (en) | Nitrogen-doped biochar and preparation method and application thereof | |
| CN112121766B (en) | Ramie fiber-based biochar and preparation method and application thereof | |
| CN107297204A (en) | A kind of TiO using NACF as carrier2The preparation method of nanometer rods photocatalysis net | |
| CN105749893A (en) | Preparation method of modified active carbon fiber with surface-loaded nanometer titanium dioxide (TiO2) | |
| CN110975918A (en) | Indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and preparation method and application thereof | |
| CN110935449A (en) | Efficient environment-friendly black titanium dioxide-based photocatalyst and preparation method thereof | |
| CN111389449A (en) | Nitrogen-doped carbon material modified silver phosphate composite photocatalyst and preparation method and application thereof | |
| CN115007208B (en) | Preparation method and application of graphene/cellulose aerogel-based composite photocatalyst | |
| CN111498952B (en) | Porous carbon iron-nickel alloy foam nickel electrode and preparation method and application thereof | |
| CN112028168A (en) | Application of tin disulfide/carbon nanofiber composite material in degradation of organic pollutants | |
| CN110732338B (en) | Carbon nanowire/g-C 3 N 4 Composite visible light catalyst and preparation method thereof | |
| Liu et al. | Cu2O nanoparticles supported on carbon nanofibers as a cost-effective and efficient catalyst for RhB and phenol degradation | |
| Zhang et al. | Enhanced charge separation of α-Bi2O3-BiOI hollow nanotube for photodegradation antibiotic under visible light | |
| Gao et al. | 3D heterogeneous CTF@ TiO 2/Bi 2 WO 6/Au hybrid supported by hollow carbon tubes and its efficient photocatalytic performance in the UV-vis range | |
| CN108117142B (en) | Flexible large-area TaON nanorod array composite BiOI carbon fiber cloth and preparation method thereof | |
| CN111672502A (en) | Method for preparing lanthanum/manganese codoped titanium oxide nanotube with photocatalytic activity by anodic oxidation | |
| CN109395759B (en) | Fe with core-shell structure3C nano particle and preparation method and application thereof | |
| CN108126726B (en) | Flexible large-area Ta3N5Nano-rod array carbon fiber cloth and preparation method thereof | |
| CN108103766A (en) | A kind of molybdenum disulfide composite fibre photochemical catalyst and preparation method for sewage disposal | |
| CN107754782B (en) | Self-supporting VO2Preparation method and product of Fenton-like catalytic material | |
| CN110787784A (en) | Silk screen type TiO2Device and method for photocatalytic degradation of VOCs (volatile organic compounds) by nanotube array | |
| CN113318732A (en) | Palladium nanoparticle-three-dimensional activated carbon composite catalyst and preparation method and application 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 |