CN114377697A - Photocatalyst with super-strong adhesion and high safety and application thereof - Google Patents
Photocatalyst with super-strong adhesion and high safety and application thereof Download PDFInfo
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- CN114377697A CN114377697A CN202210038459.5A CN202210038459A CN114377697A CN 114377697 A CN114377697 A CN 114377697A CN 202210038459 A CN202210038459 A CN 202210038459A CN 114377697 A CN114377697 A CN 114377697A
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- fiber cloth
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 70
- 239000004744 fabric Substances 0.000 claims description 69
- 239000013305 flexible fiber Substances 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 42
- 238000002791 soaking Methods 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000004917 carbon fiber Substances 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012621 metal-organic framework Substances 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 29
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000002086 nanomaterial Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000598860 Garcinia hanburyi Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910019603 Rh2O3 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229940117709 gamboge Drugs 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- 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
-
- 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
Abstract
The invention discloses a photocatalyst with super-strong adhesion and high safety and application thereof.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a photocatalyst with super-strong adhesion and high safety and application thereof.
Background
The photocatalyst technology has been developed as an environmentally friendly environmental purification technology, and can be used in any place in the world as long as light is available, and the photocatalyst has many advantages that almost all harmful organic matters can be decomposed and harmlessly treated under the irradiation of light, toxic drugs or fossil fuels such as coal and petroleum are not used, diffused environmental pollutants can be safely and effectively treated only by using clean and inexhaustible solar energy, and semipermanently recycled, and the like, so that the photocatalyst technology can be expected to be developed in the future. The photocatalyst is a bright point in the environmental purification technology because it can remove and purify environmental pollutants at a low concentration by using only the light energy of sunlight and the like without consuming global energy and using harmful chemicals, and can also be applied as an antibacterial agent and a mildew preventive.
Zinc oxide based photocatalytic materials have been found as early as the 30 s in the 20 th century. In 1968, the teaching of the japanese scholars gamboge showa finds that titanium dioxide under ultraviolet irradiation can decompose water into hydrogen and oxygen, opens the application of titanium dioxide in the field of photocatalysis, and the technology for preparing photocatalyst mostly adopts semiconductor titanium dioxide, thereby opening the door of titanium dioxide as photocatalyst. In 1976, Garey et al developed the application of photocatalysts in the environmental protection field, and utilized photocatalysis to degrade pollutants in water. From now on, the application field of the semiconductor photocatalyst material is expanded, and the conversion of light energy into other energy becomes a main research direction. The commonly used photocatalytic material is mainly an n-type semiconductor material and has the characteristics of low forbidden band width and the like. The most commonly used semiconductor material is titanium dioxide, because its band position and surface structure are referred to as the most efficient catalysts. It has excellent dispersivity and weather resistance, and has the advantages of being antibacterial, self-cleaning, anti-aging, etc. However, the energy band structure of titanium dioxide determines the light absorption range, the forbidden band width is 3.2eV, and therefore, only ultraviolet light with the wavelength of less than 387.5nm can be absorbed by the titanium dioxide. In addition, the ultraviolet light only accounts for about 5% of the sunlight, and the utilization rate is too low.
The main raw material of the photocatalyst for organic matter treatment is metal compound. The system mainly comprises a light sensor (Ru or Rp compound) and an electron transmission Medium (MV)2+Or Ru (bpy)3 2+) Donor electrons (TEOA or EDTA), surfactants and additional substances. The metalloporphyrin derivative is used as a photocatalyst to prevent reverse reaction, so that the efficiency, stability and repeatability of photocatalyst hydrogen production can be effectively improved. Meanwhile, the semiconductor nano-particles are also used as the main raw material for treating the photocatalyst organic pollutants. Because the semiconductor photocatalyst is easy to be produced in large scale, the photocatalyst film is formed by a chemical synthesis method, and comprises ZnS, methanol and water, and the C-C bond is dehydrogenated to generate hydrogen and ethanol under the action of illumination. The research has great conversion to the hydrogen conversion efficiency, and the separation rate of the ethanol reaches 95 percent, which reaches the leading level of the state.
Wherein CdS is a semiconductor catalyst widely used for degrading organic pollutants, RuO for photodegrading CdS surface2Or Rh2O3The method can rapidly separate and transmit electrons and holes generated by light, and effectively avoid photo corrosion of CdS. However, cadmium sulfide has certain physical toxicity and certain harmfulness to human health and environment. And the titanium dioxide has the characteristics of super-hydrophilicity, no toxicity, light resistance, proper energy band structure and the like, so that the photocatalyst material based on the titanium dioxide is produced. The first generation of photocatalyst material is mainly used for controlling the shape and size of crystals and the growth of the crystals of titanium dioxide under medium-high temperature conditions; rutile or anatase titanium dioxide crystals are obtained at different temperatures. The pure-phase titanium dioxide photocatalyst is sensitive to ultraviolet light and has high degradation efficiency. The second generation of photocatalyst material is formed by doping ions such as Ag +, Au +, and the like into a titanium dioxide material, so that the degradation efficiency of the photocatalyst in a visible light range is improved; the preparation method of the material is complex, the technology is relatively mature, but the industrialization difficulty is high. Therefore, on the premise of improving the absorption efficiency of visible light, the search for a novel photocatalyst material with simple procedure, low cost and wide market application range becomes a main demand for researchers to explore the field of photocatalysis.
Chinese patent CN 108706644A discloses a cyclodextrin/photocatalyst composite modified carbon-based water purifying agent, which is prepared from the following substances in parts by weight: 80-150 parts of orange peel, 20-40 parts of beta-cyclodextrin, 5-6 parts of chloroacetic acid, 30-60 parts of polyvinyl alcohol, 5-10 parts of N-methyl formamide, 1-3 parts of initiator, 0.1-0.5 part of soluble metal salt, 10-30 parts of organic titanate, 2-6 parts of silane coupling agent and 50-60 parts of solvent. The water purifying agent integrates the functions of adsorption, flocculation, catalytic degradation and the like by compounding the porous carbon, the grafted amphoteric beta-cyclodextrin and the modified titanium dioxide, thereby achieving the function of purifying water in multiple directions. The raw materials of the invention have wide sources, low cost and wide application range, and have wide application prospect; chinese patent CN 111841518A discloses a composite photocatalyst and a photocatalyst material, which comprises the following components in percentage by weight: 60-90% of modified nano titanium dioxide, 10-30% of nano diatom ooze, 2-10% of nano silver and 0.1-1% of essence, wherein the surface of the modified nano titanium dioxide particles is coated with nano silicon dioxide to form a porous coating layer. The composite photocatalyst contains nano diatom ooze and modified nano titanium dioxide, the nano diatom ooze has strong adsorption capacity, the modified nano titanium dioxide forms a porous coating layer on the surface of titanium dioxide nanoparticles, the problem that the nano titanium dioxide is easy to agglomerate is solved, the components of the nano diatom ooze are also beneficial to enabling the modified nano titanium dioxide to be more dispersed, the composite photocatalyst also contains nano silver, and the nano silver can play a role in sterilization under the condition of no light, so that the application range and the use effect of the composite photocatalyst are improved. The adsorption and catalysis functions of the photocatalyst in the prior art are gradually improved, but a part of toxic intermediate products are still generated in the decomposition process, so that the preparation of the photocatalyst material with high adsorption performance, no toxicity, no harm and environmental protection is particularly important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a photocatalyst with super-strong adhesion and high safety and application thereof.
The photocatalyst with super-strong adhesion and high safety is prepared by the following method:
s1 pre-treating the flexible fiber cloth;
s2 preparation of flexible fiber cloth-BiOBr material.
Further, the photocatalyst with super-strong adhesion and high safety is prepared by the following method:
s1 pretreatment of the flexible fiber cloth: ultrasonically cleaning flexible carbon fiber cloth in a mixed solution of water, ethanol and acetone for 30-40 min, and then drying at 60-65 ℃ for 2-3 h;
s2 preparation of flexible fiber cloth-BiOBr material: adding 2.5-3 mmol of Bi (NO)3)3·5H2O dissolved in 40 ℃Forming a solution-A in 50mL of N, N-dimethylformamide, stirring for 30-40 min at 300-400 rpm, dissolving 2.5-3 mmol of KBr in 40-50 mL of water to serve as a solution-B, soaking the flexible fiber cloth treated in the step S1 in the solution-A for 2-4 min, taking out the flexible fiber cloth, soaking the flexible fiber cloth in water for 15-20S, taking out the flexible fiber cloth, soaking the flexible fiber cloth in the solution-B for 2-4 min, taking out the flexible fiber cloth, soaking the flexible fiber cloth in water for 15-20S, repeating the four soaking steps for 4-5 times, taking out the flexible fiber cloth, drying the flexible fiber cloth at 60-65 ℃ for 2-3 h, and simultaneously drying 0.4-0.5 mmol of Bi (NO)3)3·5H2Dissolving O and 0.4-0.5 mmol KBr in 20-30 mL of ethylene glycol to obtain a mixed solution-C, transferring the soaked flexible fiber cloth and the mixed solution-C into a 25-50 mL high-pressure autoclave lined with polytetrafluoroethylene to react to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol once respectively.
Further, the volume ratio of water, ethanol and acetone in step S1 is 1: 1: 1.
further, the ratio of the flexible fiber cloth to the mixed solution of water, ethanol and acetone in step S1 is 1: (15-20) g/mL.
Furthermore, the ultrasonic power in the step S1 is 50-100W, and the frequency is 50-80 kHz.
Further, in the step S2, the reaction temperature in the autoclave is 135-140 ℃, and the reaction time is 12-14 hours.
Most preferably, the photocatalyst with super-strong adhesion and high safety is prepared by the following method:
s1 pretreatment of the flexible fiber cloth: ultrasonically cleaning flexible carbon fiber cloth in a mixed solution of water, ethanol and acetone for 30-40 min, and then drying at 60-65 ℃ for 2-3 h;
s2 preparation of flexible fiber cloth-BiOBr material: adding 2.5-3 mmol of Bi (NO)3)3·5H2Dissolving O in 40-50 mL of N, N-dimethylformamide to form a solution-A, stirring at 300-400 rpm for 30-40 min, dissolving 2.5-3 mmol of KBr in 40-50 mL of water to serve as a solution-B, soaking the flexible fiber cloth treated in the step S1 in the solution-A for 2-4 min, taking out and soaking in water for 15-20S, taking out and soaking in the solution-B for 2-4 min,taking out and soaking in water for 15-20 s, repeating the four steps of soaking for 4-5 times, taking out the flexible fiber cloth, drying at 60-65 ℃ for 2-3 h, simultaneously weighing 480-500 mg of NaBr and 200-220 mg of IRMOF-8 metal organic framework material, dissolving in 45-50 mL of water, carrying out ultrasonic treatment for 20-30 min to obtain a solution D, weighing 1940-2000 mg of Bi (NO)3)3·5H2Dissolving O in 10-12 mL of glacial acetic acid, adding the glacial acetic acid into the solution D, stirring at 400-600 rpm for 10-30 min, transferring the mixture into a hydrothermal reaction kettle, reacting at 100-110 ℃ for 7-8 h to obtain a solution-E, cooling, transferring the soaked flexible fiber cloth and the mixed solution-E into a 25-50 mL autoclave lined with polytetrafluoroethylene to react to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol once respectively.
Further, the volume ratio of water, ethanol and acetone in step S1 is 1: 1: 1.
further, the ratio of the flexible fiber cloth to the mixed solution of water, ethanol and acetone in step S1 is 1: (15-20) g/mL.
Furthermore, the ultrasonic power in the step S1 is 50-100W, and the frequency is 50-80 kHz.
Further, in the step S2, the reaction temperature in the autoclave is 135-140 ℃, and the reaction time is 12-14 hours.
The BiOBr nano-scale is used as a visible light driven photocatalyst and shows excellent light absorption performance and photocatalytic activity. Although such a photocatalyst has excellent photodegradation properties, its practical application is limited due to a complicated recovery process. Therefore, it is necessary to fix the nanomaterial on the substrate to improve recyclability. There are two main methods for immobilizing semiconductor nanomaterials. The first method is to fix the nanomaterial on a planar substrate glass or metal foil. However, practical applications of these photocatalysts are limited by their high production costs and low flexibility. The second method is to grow nanomaterials on nonwovens by electrospinning techniques. However, these nonwovens are fragile and have limited practical applications.
The carbon fiber cloth has excellent conductivity, flexibility and mechanical strength, and the inventor finds that the BiOBr photocatalyst prepared on the flexible carbon fiber cloth can be used for photodegrading various pollutants in wastewater, is environment-friendly and recyclable, has strong adsorbability, and can effectively remove over 92 percent of chemical oxygen demand in acrylic resin production wastewater.
The invention also provides application of the photocatalyst with super-strong adhesion and high safety in organic pollutant degradation, wherein the photocatalyst is used in an organic pollutant pollution area, and then a xenon lamp with the power of 500W is used for illumination for purifying organic pollutants.
Detailed Description
Partial raw material introduction in the examples:
flexible carbon fiber cloth, (900) square meter per gram, which is purchased from Nantong Senyou carbon fiber Co., Ltd;
Bi(NO3)3·5H2o, CAS: 10035-06-0, 100 mesh, available from New materials science and technology Limited of Western Farmaceae;
IRMOF-8 metal organic framework material, CAS: 473981-43-0, available from Shanghai Shutsu chemical science and technology, Inc.
Example 1
The preparation of photocatalyst with super strong adhesion and high safety includes the following steps:
s1 pretreatment of the flexible fiber cloth: taking 10g of flexible carbon fiber cloth, ultrasonically cleaning the flexible carbon fiber cloth in a mixed solution of 50mL of water, 50mL of absolute ethyl alcohol and 50mL of acetone at the frequency of 75kHz for 30min, and then drying the flexible carbon fiber cloth at 65 ℃ for 3 h;
s2 preparation of flexible fiber cloth-BiOBr material: 3mmol of Bi (NO)3)3·5H2Dissolving O in 50mL of N, N-dimethylformamide to form a solution-A, stirring at 400rpm for 40min, dissolving 3mmol of KBr in 50mL of water to obtain a solution-B, soaking the flexible fiber cloth treated in the step S1 in the solution-A for 4min, taking out and soaking in water for 20S, taking out and soaking in the solution-B for 4min, taking out and soaking in water for 20S, repeating the four soaking steps for 5 times, taking out and drying the flexible fiber cloth at 65 ℃ for 3h, and simultaneously drying 0.5mmol of Bi (NO) at the same time3)3·5H2O and 0.5mmol KBr in 30mL ethylene glycolAnd transferring the soaked flexible fiber cloth and the mixed solution-C into a 50mL autoclave with a polytetrafluoroethylene lining, reacting for 12h at 135 ℃ to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol for one time respectively.
Example 2
The preparation of photocatalyst with super strong adhesion and high safety includes the following steps:
weighing 500mg NaBr and 200mg IRMOF-8 metal organic framework material, dissolving in 50mL water, performing ultrasonic treatment for 30min to obtain solution D, weighing 1940mg Bi (NO)3)3·5H2Dissolving O in 10mL of glacial acetic acid, adding the solution D into the solution D, stirring the solution D at 400rpm for 30min, transferring the solution D into a hydrothermal reaction kettle, reacting the solution D at 100 ℃ for 8h, centrifuging the solution D at 5000rpm for 10min, removing supernatant, washing the solution D with absolute ethyl alcohol and distilled water respectively, and drying the solution D at 80 ℃ for 8h to obtain the modified BiOBr nano material.
Example 3
The preparation of photocatalyst with super strong adhesion and high safety includes the following steps:
s1 pretreatment of the flexible fiber cloth: taking 10g of flexible carbon fiber cloth, ultrasonically cleaning the flexible carbon fiber cloth in a mixed solution of 50mL of water, 50mL of absolute ethyl alcohol and 50mL of acetone at the frequency of 75kHz for 30min, and then drying the flexible carbon fiber cloth at 65 ℃ for 3 h;
s2 preparation of flexible fiber cloth-BiOBr material: 3mmol of Bi (NO)3)3·5H2Dissolving O in 50mL of N, N-dimethylformamide to form a solution-A, stirring at 400rpm for 40min, dissolving 3mmol of KBr in 50mL of water to obtain a solution-B, soaking the flexible fiber cloth treated in the step S1 in the solution-A for 4min, taking out and soaking in water for 20S, taking out and soaking in the solution-B for 4min, taking out and soaking in water for 20S, repeating the soaking method for 5 times, taking out and drying the flexible fiber cloth at 65 ℃ for 3h, simultaneously weighing 480mg of NaBr and 200mg of IRMOF-8 metal organic framework material, dissolving in 50mL of water, ultrasonically treating for 30min to obtain a solution D, and weighing 1940mg of Bi (NO) (NO is weighed)3)3·5H2Dissolving O in 10mL of glacial acetic acid, adding the solution into the solution D, stirring at 400rpm for 30min, and transferring the solution into a hydrothermal reaction kettle for 10minReacting at 0 ℃ for 8h to obtain a solution-E, cooling, transferring the soaked flexible fiber cloth and the mixed solution-E into a 50mL autoclave lined with polytetrafluoroethylene to react at 135 ℃ for 12h to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol once respectively.
Example 4
The preparation of photocatalyst with super strong adhesion and high safety includes the following steps:
s1 pretreatment of the flexible fiber cloth: taking 10g of flexible carbon fiber cloth, ultrasonically cleaning the flexible carbon fiber cloth in a mixed solution of 50mL of water, 50mL of absolute ethyl alcohol and 50mL of acetone at the frequency of 75kHz for 30min, and then drying the flexible carbon fiber cloth at 65 ℃ for 3 h;
s2 preparation of flexible fiber cloth-BiOBr material: 3mmol of Bi (NO)3)3·5H2Dissolving O in 50mL of N, N-dimethylformamide to form a solution-A, stirring at 400rpm for 40min, dissolving 3mmol of KBr in 50mL of water to obtain a solution-B, soaking the flexible fiber cloth treated in the step S1 in the solution-A for 4min, taking out and soaking in water for 20S, taking out and soaking in the solution-B for 4min, taking out and soaking in water for 20S, repeating the soaking method for 5 times, taking out and drying the flexible fiber cloth at 65 ℃ for 3h, simultaneously weighing 480mg of NaBr and 300mg of IRMOF-8 metal organic framework material, dissolving in 50mL of water, ultrasonically treating for 30min to obtain a solution D, and weighing 1940mg of Bi (NO) (NO is weighed)3)3·5H2Dissolving O in 10mL of glacial acetic acid, adding the glacial acetic acid into the solution D, stirring for 30min at 400rpm, transferring the mixture into a hydrothermal reaction kettle, reacting for 8h at 100 ℃ to obtain a solution-E, cooling, transferring the soaked flexible fiber cloth and the mixed solution-E into a 50mL autoclave lined with polytetrafluoroethylene, reacting for 12h at 135 ℃ to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol once respectively.
Example 5
The preparation of photocatalyst with super strong adhesion and high safety includes the following steps:
s1 pretreatment of the flexible fiber cloth: taking 10g of flexible carbon fiber cloth, ultrasonically cleaning the flexible carbon fiber cloth in a mixed solution of 50mL of water, 50mL of absolute ethyl alcohol and 50mL of acetone at the frequency of 75kHz for 30min, and then drying the flexible carbon fiber cloth at 65 ℃ for 3 h;
s2 preparation of flexible fiber cloth-BiOBr material: 3mmol of Bi (NO)3)3·5H2Dissolving O in 50mL of N, N-dimethylformamide to form a solution-A, stirring at 400rpm for 40min, dissolving 3mmol of KBr in 50mL of water to obtain a solution-B, soaking the flexible fiber cloth treated in the step S1 in the solution-A for 4min, taking out and soaking in water for 20S, taking out and soaking in the solution-B for 4min, taking out and soaking in water for 20S, repeating the four steps of soaking for 5 times, taking out and drying the flexible fiber cloth at 65 ℃ for 3h, simultaneously weighing 480mg of NaBr and 400mg of IRMOF-8 metal organic framework material, dissolving in 50mL of water, ultrasonically treating for 30min to obtain a solution D, and weighing 1940mg of Bi (NO) (NO is weighed3)3·5H2Dissolving O in 10mL of glacial acetic acid, adding the glacial acetic acid into the solution D, stirring for 30min at 400rpm, transferring the mixture into a hydrothermal reaction kettle, reacting for 8h at 100 ℃ to obtain a solution-E, cooling, transferring the soaked flexible fiber cloth and the mixed solution-E into a 50mL autoclave lined with polytetrafluoroethylene, reacting for 12h at 135 ℃ to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol once respectively.
Comparative example 1
The preparation of photocatalyst with super strong adhesion and high safety includes the following steps:
480mg NaBr was weighed out and dissolved in 50mL of water, and 1940mg Bi (NO) was weighed out3)3·5H2Dissolving O in 10mL of glacial acetic acid, mixing the above solutions, stirring at 400rpm for 30min, transferring into a hydrothermal reaction kettle, reacting at 100 ℃ for 8h, centrifuging at 5000rpm for 10min, removing supernatant, washing with absolute ethyl alcohol and distilled water respectively, and drying at 80 ℃ for 8h to obtain the BiOBr nano material.
Test example 1
The photocatalyst with super-strong adhesion and high safety prepared in examples 1 to 5 and comparative example 1 was subjected to a methyl blue degradation test, and methyl blue was degraded under ultraviolet and visible light. The ultraviolet light source adopts a high-pressure mercury lamp of 250W, the visible light source adopts a xenon lamp of 500W, and the ultraviolet light is filtered by an optical filter. In the experiment, a high-pressure mercury lamp or xenon lamp was placed in a dark box at a distance of about 20cm from the sample. The concentration of methyl blue solution in the reaction is 10mg/L, and the concentration of photocatalyst is 1 g/L. The stirring speed is 300rpm in the form of magnetic stirring. Before illumination, the methyl blue solution added with the photocatalyst material is stirred for 30min in the dark to reach adsorption balance. After 30min, the illumination is turned on, and the irradiation time of ultraviolet light and visible light is 120min and 200min respectively. In the reaction process, 2mL of the solution was periodically taken out, the catalyst was removed by filtration through a filter (filter pore size: 0.22 μm), and the absorbance of the filtered solution was measured by a spectrophotometer to calculate the concentration. The test results are shown in Table 1.
TABLE 1 photocatalyst methyl blue degradation test result table
As can be seen from Table 1, the BiOBr material subjected to modification treatment has the best photocatalytic performance after being combined with the flexible fiber cloth in comparative examples 1-3. Carbon cloth has good electric conductivity, pliability and mechanical strength, prepares the BiOBr photocatalyst on flexible carbon cloth, can improve the adsorptivity of BiOBr photocatalyst to be favorable to the various pollutants in the photodegradation waste water, and compare exclusive use BiOBr photocatalyst material environmental protection more and easily retrieve, in addition, BiOBr material has changed its lamellar structure through IRMOF-8 metal organic frame's processing back, more is favorable to the light absorption.
Test example 2
The photocatalyst with super-strong adhesion and high safety prepared in examples 1 to 5 and comparative example 1 was subjected to a p-xylene degradation test, and p-xylene was selected as a target pollutant to compare the degradation of p-xylene by the photocatalyst under natural light. The irradiation with sunlight was simulated with a xenon lamp, which was placed in a dark box about 20cm from the sample during the experiment. Similarly, a certain amount of deionized water and methanol are added into a conical flask, pure paraxylene is added, the concentration of the paraxylene in the reaction is about 100mg/L, and the concentration of the photocatalyst material is 2 g/L. The stirring speed is 300rpm in the form of magnetic stirring. Before the illumination, the p-xylene solution added with the photocatalyst material is stirred for 30min in the dark to reach the adsorption balance. And after 30min, extracting a first water sample, filtering by using a filter membrane, taking 1mL of sample solution into a 20mL headspace bottle, diluting to 10mL, capping, finishing sample preparation, and taking the sample as the initial concentration of the p-xylene. And (3) opening light irradiation, wherein the light irradiation time is 120min, sampling is carried out once at intervals of 20min, the samples are prepared by the same method, and the pollutant concentration is determined by adopting a headspace GC-MS method.
TABLE 2 degradation test results of p-xylene
It is seen from table 2 that the flexible fiber cloth and the BiOBr nanomaterial are combined to have higher adsorption and degradation effects on pollutants in sewage, and the flexible fiber cloth is combined to the BiOBr nanomaterial to improve light absorption, compared with the embodiment 2 that the modified BiOBr photocatalytic material is used alone to have stronger adsorption performance, so that the xylene can be effectively removed as organic pollutants, and the light absorption performance of the photocatalytic material is further improved by firstly modifying the BiOBr photocatalytic material by using an IRMOF-8 metal organic frame and then combining the modified BiOBr photocatalytic material with the flexible fiber cloth, and experiments show that the nanomaterial in example 5 shows the widest light absorption (edge: 690 nm). And the comparison of examples 3-5 shows that the increase of the dosage of the IRMOF-8 metal organic framework in the preparation process is more beneficial to the adsorption and degradation of the p-xylene by the photocatalyst.
Claims (8)
1. The photocatalyst with super-strong adhesion and high safety is characterized by being prepared by the following method:
s1 pre-treating the flexible fiber cloth;
s2 preparation of flexible fiber cloth-BiOBr material.
2. The photocatalyst with ultra-strong adhesion and high safety as claimed in claim 1, which is prepared by the following method:
s1 pretreatment of the flexible fiber cloth: ultrasonically cleaning flexible carbon fiber cloth in a mixed solution of water, ethanol and acetone for 30-40 min, and then drying at 60-65 ℃ for 2-3 h;
s2 preparation of flexible fiber cloth-BiOBr material: adding 2.5-3 mmol Bi (NO)3)3·5H2Dissolving O in 40-50 mL of N, N-dimethylformamide to form a solution-A, stirring at 300-400 rpm for 30-40 min, dissolving 2.5-3 mmol of KBr in 40-50 mL of water to serve as a solution-B, soaking the flexible fiber cloth treated in the step S1 in the solution-A for 2-4 min, taking out and soaking in water for 15-20S, taking out and soaking in the solution-B for 2-4 min, taking out and soaking in water for 15-20S, repeating the four steps of soaking for 4-5 times, taking out and drying the flexible fiber cloth at 60-65 ℃ for 2-3 h, and simultaneously, dissolving 0.4-0.5 mmol of Bi (NO) in the range of 0.4-0.5 mmol3)3·5H2Dissolving O and 0.4-0.5 mmol KBr in 20-30 mL of ethylene glycol to obtain a mixed solution-C, transferring the soaked flexible fiber cloth and the mixed solution-C into a 25-50 mL high-pressure autoclave lined with polytetrafluoroethylene to react to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol once respectively.
3. The photocatalyst with super-strong adhesion and high safety is characterized by being prepared by the following method:
s1 pretreatment of the flexible fiber cloth: ultrasonically cleaning flexible carbon fiber cloth in a mixed solution of water, ethanol and acetone for 30-40 min, and then drying at 60-65 ℃ for 2-3 h;
s2 preparation of flexible fiber cloth-BiOBr material: adding 2.5-3 mmol Bi (NO)3)3·5H2Dissolving O in 40-50 mL of N, N-dimethylformamide to form a solution-A, stirring at 300-400 rpm for 30-40 min, dissolving 2.5-3 mmol of KBr in 40-50 mL of water to obtain a solution-B, and soaking the flexible fiber cloth treated in the step S1 in the solution-A to reach 2 ℃; and then, dissolving the solution-B in water to obtain a solution-A4min, taking out and soaking in water for 15-20 s, taking out and soaking in the solution-B for 2-4 min, taking out and soaking in water for 15-20 s, repeating the four steps of soaking for 4-5 times, taking out the flexible fiber cloth, drying at 60-65 ℃ for 2-3 h, simultaneously weighing 480-500 mg of NaBr and 200-220 mg of IRMOF-8 metal organic framework material, dissolving in 45-50 mL of water, performing ultrasonic treatment for 20-30 min to obtain a solution D, weighing 1940-2000 mg of Bi (NO) (NO is not limited by the content of the metal organic framework material), and weighing3)3·5H2Dissolving O in 10-12 mL of glacial acetic acid, adding the glacial acetic acid into the solution D, stirring at 400-600 rpm for 10-30 min, transferring the mixture into a hydrothermal reaction kettle, reacting at 100-110 ℃ for 7-8 h to obtain a solution-E, cooling, transferring the soaked flexible fiber cloth and the mixed solution-E into a 25-50 mL autoclave lined with polytetrafluoroethylene to react to obtain flexible fiber cloth-BiOBr, and washing with deionized water and ethanol once respectively.
4. The ultra-strong adhesion, high safety photocatalyst as set forth in claim 2 or 3, characterized in that: the volume ratio of the water, the ethanol and the acetone in the step S1 is 1: 1: 1.
5. the ultra-strong adhesion, high safety photocatalyst as set forth in claim 2 or 3, characterized in that: the ratio of the flexible fiber cloth to the mixed solution of water, ethanol and acetone in the step S1 is 1: (15-20) g/mL.
6. The ultra-strong adhesion, high safety photocatalyst as set forth in claim 2 or 3, characterized in that: the ultrasonic power in the step S1 is 50-100W, and the frequency is 50-80 kHz.
7. The ultra-strong adhesion, high safety photocatalyst as set forth in claim 2 or 3, characterized in that: in the step S2, the reaction temperature in the autoclave is 135-140 ℃, and the reaction time is 12-14 h.
8. The use of the ultra-strong adhesion and high safety photocatalyst of claims 1-7 in the degradation of organic pollutants, wherein the photocatalyst is used in an organic pollutant pollution area and then illuminated by a xenon lamp with 500W power for purifying the organic pollutants.
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