CN114682300A - TiO loaded by MOFs structure2Method for preparing photocatalytic textile web - Google Patents
TiO loaded by MOFs structure2Method for preparing photocatalytic textile web Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 89
- 239000004753 textile Substances 0.000 title claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011941 photocatalyst Substances 0.000 claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004744 fabric Substances 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005054 agglomeration Methods 0.000 claims abstract description 5
- 230000002776 aggregation Effects 0.000 claims abstract description 5
- 230000009286 beneficial effect Effects 0.000 claims abstract description 5
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 230000006798 recombination Effects 0.000 claims abstract description 4
- 238000005215 recombination Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract 2
- 230000002708 enhancing effect Effects 0.000 claims abstract 2
- 230000002401 inhibitory effect Effects 0.000 claims abstract 2
- 239000013384 organic framework Substances 0.000 claims abstract 2
- 230000001737 promoting effect Effects 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000010865 sewage Substances 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical group CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005067 remediation Methods 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 230000006855 networking Effects 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- -1 superoxide anions Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B01J35/39—
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a MOFs structure loaded TiO2A method of making a photocatalytic textile web. The preparation method of the photocatalytic textile web related by the invention provides three schemes: firstly, preparing fabrics loaded with MOFs, and then soaking the fabrics in TiO2Dissolving in the solution and drying; scheme two, firstly preparing the supported TiO2The textile is dipped in MOFs solution and dried; scheme three, first prepare TiO2And mixing the solution with MOFs, soaking the mixture in the mixed solution and drying. The photocatalyst prepared by the invention adopts MOFs organic framework structure as a photocatalyst-loading carrier, and prevents TiO by utilizing the characteristic of large specific surface area2The agglomeration is also beneficial to inhibiting the electron hole recombination, promoting the separation of photoproduction electrons, enhancing the oxygen precipitation reaction and obviously improving the photocatalysis efficiency. The prepared photocatalysis net can be recycled, and overcomes the defects of powderThe photocatalyst is difficult to recycle.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a method for loading TiO by using MOFs structure2A method of making a photocatalytic textile web.
Background
The water pollution of urban riverways is increasingly serious because of the direct discharge of domestic sewage and untreated industrial wastewater. The black and odorous water body can release toxic gases such as hydrogen sulfide and ammonia to threaten human health, and meanwhile, a large amount of dissolved oxygen in the water can be consumed during decomposition of organic matters in the sewage, so that fishes and aquatic organisms in the water body die due to oxygen deficiency, and the ecological balance in the water body is damaged. Therefore, sewage purification is becoming a focus of research. Among them, a sewage purification method based on photocatalysis has been widely paid attention. The photocatalytic sewage treatment method generally adopts a semiconductor material photocatalyst with a photocatalytic function. When the photocatalyst is irradiated by sunlight, electrons in an internal low-energy area are excited and transited by energy, photo-generated electrons and photo-generated holes are generated in the photocatalyst, water molecules and the photo-generated holes react to generate hydroxyl radicals, and oxygen and the photo-generated electrons react to generate superoxide anions. The three active oxidation substances of hydroxyl radicals, superoxide anions and photoproduction cavities can degrade organic pollutants into carbon dioxide, water and other small molecules, achieve the effect of sewage purification, and are beneficial to increasing the content of dissolved oxygen in a water body. Titanium dioxide (TiO)2) The material is a photocatalyst which is most widely applied because of the advantages of no toxicity, low price, high degradation rate, cyclic utilization and the like.
The application mode of the photocatalyst in sewage treatment is to throw photocatalyst powder into sewage to dissolve the photocatalyst in the sewage and play a catalytic role under the irradiation of sunlight, however, the photocatalyst is often reduced in catalytic efficiency because electron holes generated by the irradiation of the sunlight are easy to recombine and the photocatalyst is agglomerated. Meanwhile, the method of throwing the photocatalyst into the water body can lead the photocatalyst to be difficult to recover, so that the purified water body contains the photocatalyst for a long time.
Aiming at the problems, the invention provides a method for preparing MOFs loaded TiO2A method of photocatalyzing a textile web. The metal organic framework Materials (MOFs) are a porous structure of a periodic net-shaped framework formed by metal ions/clusters and organic ligands through coordination self-assembly, and have the characteristics of large specific surface area, various types and structures, high porosity, adjustable structure and the like. Due to the regular periodic arrangement structure, rich active centers, high specific surface area and high porosity, the MOFs shows excellent catalytic oxygen evolution activity. TiO 2 photocatalyst2Loaded on MOFs material with large specific surface area, can solve the problem of photocatalyst TiO2Easy to agglomerate and is favorable to the separation and transfer of photogenerated electrons and holes. Effectively inhibit the recombination of photo-generated charges, enhance the oxygen precipitation activity and obviously improve the photocatalytic efficiency. In addition, preparation of MOFs-supported TiO2The photocatalytic textile net can be repeatedly used, and the problem that the powdery photocatalyst is difficult to recycle is solved. The MOFs load TiO provided by the invention2The photocatalytic textile net is not only suitable for sewage purification, but also can be widely applied to the fields of industrial waste gas purification, soil remediation, solar hydrogen production and oxygen production and the like.
Disclosure of Invention
The invention aims to provide MOFs loaded TiO2The preparation method of the photocatalytic textile net utilizes the characteristic of large specific surface area of MOFs to overcome the problems of high recombination rate of photo-generated electrons and holes, catalyst agglomeration and the like in the photocatalyst, enhances the oxygen precipitation activity and obviously improves the catalytic efficiency of the photocatalyst. Simultaneously, loading MOFs into TiO2The photocatalyst is formed by dipping the photocatalytic textile net, so that the problem that the powdery photocatalyst is difficult to recycle is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
MOFs loaded TiO2The photocatalytic textile web is made of photocatalyst TiO2The metal organic framework material MOFs and the textile are prepared by compounding.
The MOFs loads TiO2The method for preparing a photocatalytic textile web, comprising the steps of:
(1) preparing a solution of the metal organic framework MOFs material: dissolving cobalt nitrate hexahydrate or zinc nitrate hexahydrate in deionized water or methanol to obtain a solution A, and dissolving 2-methylimidazole in deionized water or methanol to obtain a solution B. And (3) after the solution A is poured into the solution B, standing for a period of time to obtain the solution of the metal organic framework MOFs.
(2)TiO2Preparing sol: slowly dripping orthotitanate into lower alcohol and simple organic acid to obtain a mixed solution C, heating and stirring at room temperature to obtain the TiO2And (3) sol.
(3) Soaking textiles in the forms of cloth, ropes and the like in a solution of a metal organic framework MOFs material to obtain the textile growing the metal organic framework MOFs material, and soaking the textile growing the metal organic framework MOFs material into TiO2Dissolving in sol; or soaking fabric in the form of cloth, rope, etc. in TiO2In sol to obtain the sol with TiO grown2Photocatalyst-containing textile, and TiO grown thereon2Soaking the textile of the photocatalyst into a solution of a metal organic framework MOFs material; or mixing the solution of the metal organic framework MOFs material with TiO2Mixing the photocatalytic sol, and soaking the fabric in the form of cloth, rope, etc. into MOFs and TiO2In the mixed solution of (1). The above steps make TiO2The photocatalytic liquid fully enters MOFs micropores on the surface of the textile fiber, and after being soaked for a period of time, the photocatalytic liquid is placed into a drying oven to be dried, so that MOFs loaded TiO is obtained2The photocatalytic textile web of (1).
Further, in the step (1), the mass percentage concentration of the solution A is 5-30%; the volume of the solution A is 2.7 ml-17.1 ml. The mass percentage concentration of the solution B is 5-30%; the volume of the solution B is 25.6-209 ml, the concentration molar ratio of the solution A to the solution B is 1: 10-1: 50, and the standing time is 0.5-6 h.
Further, in the step (2), the n-titanate is tetra-n-propyl titanate or tetra-n-butyl titanate; the lower alcohol is absolute ethyl alcohol or propanol; the simple organic acid is glacial acetic acid or n-propionic acid and the like. The pH value of the solution C is 1-3; the heating and stirring time of the solution C is 0.5-2 h, and the heating and stirring temperature is 80-180 ℃; the mass ratio of the ortho-titanate, the lower alcohol, the simple acid and the like is 13.27-24.13: 54.39-66.24: 0.71-5.13.
Further, in the step (3), the dipping time is 1-15 min; the drying time is 1-15 min; the drying temperature is 100-200 ℃.
The invention has the following beneficial effects: aiming at the problems that photo-generated charges of the photocatalyst are easy to compound, the photocatalyst agglomeration causes low catalytic efficiency and the like, the MOFs loaded TiO is provided2A photocatalytic textile web solution. The invention has two innovation points, one is that the invention adopts metal framework material MOFs with large specific surface area to load photocatalyst TiO2Is helpful to solve the problem of photocatalyst TiO2The problem of agglomeration promotes the separation and migration of generated electrons and holes, and greatly improves the photocatalytic efficiency. And secondly, the photocatalytic textile net can be repeatedly recycled, so that the difficulty that the powdery photocatalyst is difficult to recover is overcome. The MOFs load TiO provided by the invention2The photocatalytic textile net is not only suitable for sewage purification, but also can be widely applied to the fields of industrial waste gas purification, soil remediation and the like. The invention can promote the utilization of solar energy to purify waste gas and waste water, and is beneficial to the increase of economic and social benefits.
Drawings
FIG. 1 is a schematic structural diagram of a basic embodiment of the present invention
FIG. 2 is a transmission electron micrograph of MOFs prepared from cobalt nitrate hexahydrate and 2-methylimidazole of the present invention (a, scale: 100 nm; b, scale: 0.5 μm)
FIG. 3 is a transmission electron micrograph of MOFs prepared from zinc nitrate hexahydrate and 2-methylimidazole according to the present invention (a, scale: 100 nm; b, scale: 0.5 μm)
Detailed Description
The structure of the basic embodiment of this embodiment is schematically shown in fig. 1, in which: textile net 1 in the form of cloth, rope, etc., MOFs metal organic framework structure 2, TiO2A photocatalyst 3.
Example 1:
preparation of MOFs loaded TiO2The method of photocatalytic textile networking of (1), comprising the steps of:
(1) 0.9g of cobalt nitrate hexahydrate was dissolved in 6.02mL of deionized water to give a red solution A, and 11g of 2-methylimidazole was dissolved in 73.62mL of deionized water to give a solution B. And (3) after the solution A is poured into the solution B, standing for a period of time to obtain the solution of the metal organic framework MOFs material.
(2) Slowly dripping tetra-n-propyl titanate into ethanol and glacial acetic acid, wherein the mass ratio of the tetra-n-propyl titanate to the ethanol to the glacial acetic acid is 19.15: 60.02: 3.68 to obtain a mixed solution C, heating at 130 ℃, and stirring for 1h to obtain the TiO2And (3) sol.
(3) Soaking textiles in the forms of cloth, ropes and the like in a solution of a metal organic framework MOFs material to obtain the textile growing the metal organic framework MOFs material, and soaking the textile growing the metal organic framework MOFs material into TiO2In sol to make TiO2The photocatalytic liquid fully enters MOFs micropores on the surface of the textile fiber, is soaked for 10min, and is dried in a drying oven at 150 ℃ for 1h to obtain MOFs-loaded TiO2The photocatalytic textile web of (1).
Example 2
The steps are the same as example 1, except that the step (3) is changed into the step of dipping the textiles in the forms of cloth, rope and the like in TiO2In sol to obtain the sol with TiO grown2Photocatalyst-containing textile, and TiO grown thereon2Soaking the textile of the photocatalyst into the solution of the MOFs material with the metal organic framework to ensure that the TiO is2The photocatalytic liquid fully enters MOFs micropores on the surface of the textile fiber, is soaked for 10min, and is dried in a drying oven at 150 ℃ for 1h to obtain MOFs-loaded TiO2The photocatalytic textile web of (1).
Example 3
The steps are the same as example 1, except that the step (3) is changed into the step of mixing TiO and the solution of the metal organic framework MOFs material2Mixing the photocatalytic sol, and soaking the fabric in the form of cloth, rope, etc. into MOFs and TiO2In the mixed solution of (2) to make TiO2The photocatalytic liquid fully enters the textile fiber surfaceSoaking the MOFs micropores in water for 10min, and drying in a drying oven at 150 deg.C for 1h to obtain MOFs-loaded TiO2The photocatalytic textile web of (1).
Example 4
The procedure is as in example 1, except that 0.9g of cobalt nitrate hexahydrate in 6.02ml of deionized water in example 1 is replaced by 1.68g of zinc nitrate hexahydrate in 80ml of methanol; instead of 11g 2-methylimidazole dissolved in 73.62mL deionized water, 3.70g 2-methylimidazole was dissolved in 80mL methanol.
Example 5
The procedure is as in example 2, except that in example 2, 0.9g of cobalt nitrate hexahydrate is dissolved in 6.02ml of deionized water, instead, 1.68g of zinc nitrate hexahydrate is dissolved in 80ml of methanol; instead of 11g of 2-methylimidazole dissolved in 73.62mL of deionized water, 3.70g of 2-methylimidazole were dissolved in 80mL of methanol.
Example 6
The procedure is as in example 3, except that in example 3, 0.9g of cobalt nitrate hexahydrate is dissolved in 6.02ml of deionized water, instead, 1.68g of zinc nitrate hexahydrate is dissolved in 6.02ml of methanol; instead of 11g of 2-methylimidazole dissolved in 73.62mL of deionized water, 3.70g of 2-methylimidazole were dissolved in 80mL of methanol.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. MOFs structure loaded TiO2The photocatalytic textile web of (a) is characterized by: the photocatalytic textile net is loaded with TiO by MOFs structure2The MOFs organic framework structure is used as a supported photocatalyst TiO2The carrier of (2) is used for preventing catalyst TiO by using the characteristic of large specific surface area2The agglomeration is also beneficial to inhibiting the recombination of electrons and holes, promoting the separation and migration of photoproduction electrons, enhancing the oxygen precipitation reaction and obviously improving the photocatalysis efficiency.
2. A process for preparing the compound of claimSolving 1 the MOFs loaded TiO2The method of photocatalytic textile networking of (1), characterized by: the photocatalytic textile net is TiO synthesized by a hydrothermal method2The sol is loaded on an MOFs structure and a textile net and then is dried to prepare the silica sol.
3. The method according to claim 2, characterized by the steps of:
(1) preparing a solution of the metal organic framework MOFs material: dissolving cobalt nitrate hexahydrate or zinc nitrate hexahydrate in deionized water or methanol to obtain a solution A, and dissolving 2-methylimidazole in deionized water or methanol to obtain a solution B. And (3) after the solution A is poured into the solution B, standing for a period of time to obtain the solution of the metal organic framework MOFs.
(2)TiO2Preparing sol: slowly dripping orthotitanate into lower alcohol and simple organic acid to obtain a mixed solution C, heating and stirring at room temperature to obtain the TiO2And (3) sol.
(3) Soaking textiles in the forms of cloth, rope and the like in a solution of a metal organic framework MOFs material to obtain the textile growing the metal organic framework MOFs material, and soaking the textile in TiO2Dissolving in sol; or soaking fabric in the form of cloth, rope, etc. in TiO2In sol to obtain the sol with TiO grown2Soaking the fabric in the forms of cloth, rope and the like into the solution of the MOFs material with the metal-organic framework; or mixing the solution of the metal organic framework MOFs material with TiO2Mixing the photocatalytic sol, and soaking the textile into MOFs and TiO2In the mixed solution of (1). The above steps make TiO2The photocatalytic liquid fully enters MOFs micropores on the surface of the textile fiber, and after being soaked for a period of time, the photocatalytic liquid is placed into a drying oven to be dried, so that MOFs loaded TiO is obtained2The photocatalytic textile web of (1).
4. The MOFs loaded with TiO according to claim 32The method for preparing the photocatalytic textile web is characterized by comprising the following steps: in the step (1), the mass percentage concentration of the solution A is 5-30%; the body of solution AThe volume is 2.7ml to 17.1 ml. The mass percentage concentration of the solution B is 5-30%; the volume of the solution B is 25.6-209 ml, the molar ratio of the solution A to the solution B is 1: 10-1: 50, and the standing time is 0.5-6 h.
5. The MOFs loaded with TiO according to claim 32The method for preparing the photocatalytic textile web is characterized by comprising the following steps: in the step (2), the n-titanate is tetra-n-propyl titanate or tetra-n-butyl titanate; the lower alcohol is absolute ethyl alcohol or propyl alcohol; the simple organic acid is glacial acetic acid or n-propionic acid and the like. The pH value of the mixed solution C is 1-3; the heating and stirring time of the solution C is 0.5-2 h, and the heating and stirring temperature is 80-180 ℃; the mass ratio of the ortho-titanate to the lower alcohol to the simple acid is 13.27-24.13: 54.39-66.24: 0.71-5.13.
6. The MOFs loaded with TiO according to claim 32The preparation method of the photocatalytic textile web is characterized in that in the step (3), the dipping time is 1-15 min; the drying time is 1-15 min; the drying temperature is 100-200 ℃.
7. A MOFs loaded with TiO according to claim 12The photocatalytic textile net is not only suitable for sewage purification, but also can be used in the fields of industrial waste gas purification, soil remediation, solar hydrogen production and oxygen production and the like.
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