CN107096556B - preparation method of visible light response TiO2 precursor, TiO2 precursor and catalyst - Google Patents
preparation method of visible light response TiO2 precursor, TiO2 precursor and catalyst Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000002243 precursor Substances 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000004298 light response Effects 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010992 reflux Methods 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004327 boric acid Substances 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 229920000620 organic polymer Polymers 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 23
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 21
- 238000005336 cracking Methods 0.000 claims description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 28
- 239000000835 fiber Substances 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 8
- 238000005470 impregnation Methods 0.000 abstract description 5
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- 230000001699 photocatalysis Effects 0.000 description 19
- 239000000843 powder Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910052796 boron Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 238000013032 photocatalytic reaction Methods 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910011210 Ti—O—N Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RULKYXXCCZZKDZ-UHFFFAOYSA-N 2,3,4,5-tetrachlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C(Cl)=C1Cl RULKYXXCCZZKDZ-UHFFFAOYSA-N 0.000 description 1
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/068—Polyalkylene glycols
-
- B01J35/39—
-
- B01J35/615—
-
- 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
- C02F2101/38—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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 relates to a preparation method of a visible light response TiO2 precursor, and the obtained TiO2 precursor and a catalyst, wherein the preparation method comprises the following steps: 1) placing titanate and organic polymer in a reaction container, adding boric acid at 50-90 ℃, and reacting at 100-120 ℃ until the solution is clear and transparent; 2) adding nitrogen-containing compound at room temperature to 90 ℃, and heating and refluxing; 3) adding a chelating agent at room temperature to 100 ℃, and heating and refluxing; 4) dripping the mixed solution of water and alcohol at room temperature to 80 ℃, refluxing after dripping, reducing the temperature and removing the solvent to obtain the product. The TiO2 precursor can be dissolved in a common solvent, so that the precursor can be loaded on a fiber, a molecular sieve and other matrixes by simple impregnation, the matrix loaded with the precursor is sintered at high temperature in the air, and the precursor is converted into a TiO2 photocatalyst to be loaded on the matrix, thereby solving the problem of recovery of the catalyst and the problem of no response of the common TiO2 catalyst to visible light.
Description
Technical Field
The invention belongs to the field of material science, and particularly relates to a preparation method of a visible light response TiO2 precursor, an obtained TiO2 precursor and a catalyst.
Background
Since the twentieth century, with the continuous development and progress of science and technology, the global industry has been unprecedented. However, the development of industry has promoted economic development and facilitated human life, but has also destroyed the environment where human lives in an inexorable manner, and the influence of air pollution and water pollution caused by the development of industry on human life has become more and more obvious. The photocatalytic oxidation technology based on semiconductor catalyst is increasingly receiving attention from scholars at home and abroad as an advanced oxidation technology. Almost all organic matters can be completely oxidized into simple inorganic matters such as CO2 and H2O under the action of photocatalysis, and in addition, the photocatalyst can also reduce heavy metal ions in water. Among the commonly used semiconductor photocatalysts, TiO2 has the advantages of high activity, good stability, no secondary pollution, no harm to human bodies, low price and the like, can selectively mineralize various organic pollutants, and becomes the photocatalyst which is most valued and has wide application prospect.
The photocatalytic properties of TiO2 semiconductors have been confirmed by many studies, but two key problems need to be solved to move to practical use: the traditional photocatalytic research is generally carried out in a suspended state photocatalytic reaction system, and the problems that TiO2 powder is easy to agglomerate, the continuous separation, recovery and recycling of the catalyst are difficult to realize, and the like exist; secondly, the photocatalytic oxidation of TiO2 can be carried out only within the limited wavelength range of ultraviolet light, and the proportion of sunlight is low, thus limiting the popularization and application of the photocatalytic technology. Therefore, the immobilization of the catalyst and the reaction of the TiO2 under visible light by changing the property have great practical significance for the application of the photocatalytic oxidation technology in air purification and water treatment.
preparation and characterization of visible light active TiO2 [ zhao dan, hui li, etc. ] preparation and characterization of visible light active TiO2 [ J ], proceedings of the tianjin city institute of construction, 3 months 2010, vol 16, No. 1: 33-36 nanometer Ti-O-N photocatalyst with visible light activity is prepared by taking TiOSO4 and ammonia water as raw materials through a chemical precipitation method, the performance of the nanometer Ti-O-N photocatalyst is characterized by adopting detection methods such as SEM, BET, XRD, UV-vis, ESR, XPS and the like, the catalytic activity of the photocatalyst under visible light is researched through a methyl orange solution degradation experiment, the influence of factors such as specific surface area, visible light absorption intensity, crystal structure and the like on the photocatalytic activity of the photocatalyst is discussed, the prepared nanometer Ti-O-N photocatalyst can strongly absorb visible light with the wavelength range of 400-600nm after heat treatment, and the visible light absorption intensity is closely related to the heat treatment temperature of powder. The photocatalysis test shows that: the photocatalyst after heat treatment at 400 ℃ has the strongest absorption to visible light, relatively larger specific surface area and more complete developed crystal structure, and therefore, the photocatalyst shows the best photocatalytic activity under the visible light. However, the obtained catalyst exists in a powder form, which is not beneficial to the recycling of the catalyst, and even if the catalyst is recycled, the catalyst is easy to agglomerate when being used for the second time after being recycled, so that the photocatalytic performance is reduced, and the utilization rate of titanium dioxide in unit mass is low.
jixiang Yuan et al [ Yuan, J., et al ] "Doping mode, band structure and photocatalytic mechanism of B-N-coded TiO2." Applied Surface Science,2011,257(16): 7335) 7342 ] synthesized an N, B-codoped TiO2 catalyst by a sol-gel method using ammonia and boric acid as N source and B source, respectively. The photocatalysis test shows that: the degradation rate (78.2% + -1.2%) of N, B co-doped TiO2 catalyst to tetrachlorophenol under visible light irradiation far exceeds that of B and N single doped catalyst and undoped catalyst (B-TiO 2: 31% + -0.8%, N-TiO 2: 26.9% + -0.5%, undoped TiO 2: 9.1% + -0.2%). However, the obtained catalyst exists in a powder form, which is not beneficial to the recycling of the catalyst, and even if the catalyst is recycled, the catalyst is easy to agglomerate when being used for the second time after being recycled, so that the photocatalytic performance is reduced, and the utilization rate of titanium dioxide in unit mass is low.
In conclusion, the TiO2 photocatalyst prepared by the prior art generally exists in a powder form, the photocatalytic reaction is generally carried out in a suspended state photocatalytic reaction system, and the problems of difficult sedimentation, great recovery difficulty, easy agglomeration of TiO2 powder, difficulty in realizing continuous separation, recovery and recycling of the catalyst and the like exist; related research on loading of powder is also carried out, but the problems of uneven loading and easy powder falling generally exist; moreover, the ordinary TiO2 catalyst only responds to ultraviolet light, and the ultraviolet light part in sunlight only accounts for less than 5%, so that the problem seriously limits the application of the TiO2 photocatalyst in practice. The polymer precursor has the advantages of adjustable structure, adjustable components, convenient doping, good film forming property, easy soft template compounding and the like, and has certain advantages in the aspect of preparing supported photocatalysts, visible light responsive photocatalysts and coatings.
in the patent application No. 201610017971.6, the present applicant discloses a method for preparing a precursor of N-doped TiO2, which comprises the following steps: 1) putting titanate into a reaction container, adding a nitrogen-containing compound, and heating and refluxing; 2) adding a chelating agent at room temperature to 100 ℃, and heating and refluxing; 3) and (3) dripping a mixed solution of water and alcohol at the room temperature of 80 ℃, refluxing after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the TiO2 precursor. The visible light responding TiO2 precursor provided by the invention can be dissolved in a common solvent, so that the precursor can be loaded on a fiber, a sheet, a porous material (such as a molecular sieve) and other matrixes by simple impregnation, then the matrix loaded with the precursor is sintered at high temperature in the air, and the precursor is converted into a visible light responding TiO2 photocatalyst to be loaded on the matrix, thereby solving the problem of catalyst recovery and the problem of no response of a common TiO2 catalyst to visible light. The product obtained after cracking the precursor has good photocatalytic capability under visible light, and under the irradiation of a 500W xenon lamp, the degradation rate of trichlorophenol is 56% within 5h, and the degradation rate of methyl orange is 52.1%. Although the invention solves the problems of recycling of the catalyst and visible light response, the visible light catalytic activity is still required to be further improved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
the invention aims to overcome the defects and provide a preparation method of a visible light response TiO2 precursor. The precursor prepared by the preparation method provided by the invention is a high molecular organic compound, has the processing characteristic of organic high molecules, can be loaded on a fiber, a sheet or a porous material (such as a molecular sieve) and other matrixes by simple impregnation, then the matrix loaded with the precursor is sintered at high temperature in the air, the precursor is inorganic and is converted into a visible light-responsive TiO2 photocatalyst to be loaded on the matrix, and the problem of catalyst recovery and the problem of no response of a common TiO2 catalyst to visible light are solved. In addition, the invention also introduces the high molecular chain segment into the molecular structure of the precursor, and the high molecular chain segment is cracked in the inorganic process of the precursor, so that the obtained TiO2 photocatalyst has a porous structure, the specific surface area of the catalyst is improved, and the photodegradation efficiency is favorably improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a visible light responding TiO2 precursor comprises the following steps:
1) Placing titanate and organic polymer in a reaction container, adding boric acid at 50-90 ℃, and reacting at 100-120 ℃ until the solution is clear and transparent;
2) adding nitrogen-containing compound at room temperature to 90 ℃, and heating and refluxing;
3) Adding a chelating agent at room temperature to 100 ℃, and heating and refluxing;
4) And (3) dripping a mixed solution of water and alcohol at the room temperature of 80 ℃, refluxing after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the visible light response TiO2 precursor.
In the prior art, a TiO2 photocatalyst generally exists in a powder form, a photocatalytic reaction is generally carried out in a suspended state photocatalytic reaction system, and the problems of difficult sedimentation, great recovery difficulty, easy agglomeration of TiO2 powder, difficulty in realizing continuous separation, recovery and recycling of the catalyst and the like exist; related research on loading of powder is also carried out, but the problems of uneven loading and easy powder falling generally exist; moreover, the ordinary TiO2 catalyst only responds to ultraviolet light, and the ultraviolet light part in sunlight only accounts for less than 5%, so that the problem seriously limits the application of the TiO2 photocatalyst in practice.
in the prior art, when B-doped titanium oxide is synthesized, boric acid is often required to be dissolved in water, and the boric acid is low in solubility, so that the boric acid is dissolved by using more water, which easily causes uncontrollable hydrolysis process of titanate and easy gelation of a reaction system.
in the invention, firstly titanate and organic polymer are placed in a reaction vessel, boric acid particles are directly added at 50-90 ℃, heating reaction is carried out at 120 ℃ of 100 ℃ and the temperature is 120 ℃, the system is clear and transparent, then nitrogen-containing compound is added at room temperature-90 ℃, chelating agent is added at room temperature-100 ℃ after heating reflux is carried out for a period of time, then mixed solution of water and alcohol is dripped at room temperature-80 ℃ after heating reflux is carried out for a period of time, visible light response TiO2 photocatalyst precursor is obtained after temperature reduction and decompression removal of solvent, the precursor is a polymer organic compound which has the processing characteristics of organic polymer and can be dissolved in common solvent, therefore, the precursor-loaded matrix can be loaded on fiber, sheet or porous material (such as molecular sieve) by simple impregnation, and then the precursor-loaded matrix is sintered at high temperature in the air, the precursor is subjected to inorganic reaction, and the TiO2 photocatalyst which is converted into visible light response is loaded on the substrate, so that the problem of catalyst recovery is solved, and the problem that the common TiO2 catalyst does not respond to visible light is solved. Meanwhile, the high molecular chain segment is introduced into the molecular structure of the precursor, and the high molecular chain segment is cracked in the inorganic process of the precursor, so that the obtained TiO2 photocatalyst has a porous structure, the specific surface area of the catalyst is increased, and the photodegradation efficiency is favorably improved.
Because of the viscosity of titanate, if boric acid is directly added into the system at room temperature, the boric acid is agglomerated together, and a clear and transparent solution cannot be formed, so that the reaction cannot be carried out. According to the invention, boric acid particles are directly added into the system at 50-90 ℃, so that the problem that the hydrolysis process of titanate is difficult to control due to the use of water is avoided, the addition of boric acid before the reaction of titanate, a nitrogen source and a chelating agent is favorable for ensuring that low-activity boric acid can be fully reacted with titanate, and meanwhile, after multiple experiments, the boric acid is added at 50-90 ℃, so that the boric acid is easy to disperse in the system for reaction.
The invention prepares a TiO2 precursor containing a polymer chain segment, boron and nitrogen in a molecular structure, the specific surface area of a product obtained by cracking the precursor is as high as 220m2/g (the specific surface area of the product without organic polymer is 100m2/g), the product has better photocatalytic capacity under ultraviolet light (the degradation rate of methyl orange in 30min under the irradiation of a 500W high-pressure mercury lamp is 100%), and the product has good photocatalytic capacity under visible light (the degradation rate of methyl orange in 4h under the irradiation of a 500W xenon lamp is 87.1%).
The molar ratio of the boric acid to the titanate is (0.04-0.3): 1.
The mass of the organic polymer is 0.1 to 3 times of the mass of Ti atoms in the system.
In the step 1), the organic polymer is one or a mixture of polyethylene glycol, polypropylene glycol, polymethyl methacrylate and polyvinylpyrrolidone.
the molar ratio of the titanate, the nitrogen-containing compound, the chelating agent and the water is 1: (0.1-3): (0.1-1): (0.8 to 1.3).
The molar ratio of titanate, organic polymer, boric acid, nitrogen-containing compound, chelating agent and water is not properly selected, so that a soluble precursor cannot be obtained, and precipitates can appear in the reaction process. Through a large number of tests, the invention determines that the molar ratio of titanate, boric acid, nitrogen-containing compound, chelating agent and water is 1: (0.04-0.3): (0.1-3): (0.1-1): (0.8 to 1.3), the mass of the organic polymer is 0.1 to 3 times of the mass of Ti atom in the system. Within this molar ratio range, a soluble precursor can be obtained.
The molar ratio of water to alcohol in the mixed solution of water and alcohol is 1 (3-20).
The heating reflux time in the step 2) is 0.5-5 h; the heating reflux time in the step 3) is 0.5-5 h; and 4) refluxing for 1-8 h.
In the step 1), the titanate is one or a mixture of more of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate or tetraisobutyl titanate.
In the step 2), the nitrogen-containing compound is one or a mixture of more of ethanolamine, acetamide, N-dimethylacetamide, glycine or alanine, preferably ethanolamine, acetamide or N, N-dimethylacetamide.
in the step 3), the chelating agent is one or a mixture of acetylacetone and ethyl acetoacetate.
In the step 4), in the mixed solution of water and alcohol, the alcohol is one or a mixture of ethanol, n-propanol, isopropanol, n-butanol or isobutanol.
It is also an object of the present invention to provide a visible light responsive TiO2 precursor.
The visible light responding TiO2 precursor is prepared by the preparation method.
The visible light responding TiO2 precursor is dissolved in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
the method comprises the steps of dissolving the visible-light-responsive TiO2 precursor in n-propanol, controlling the Ti content of the solution to be 1-3%, then soaking quartz fiber cotton, and curing and cracking to obtain the quartz fiber-loaded visible-light-responsive TiO2 catalyst.
In the invention, the visible light responding TiO2 precursor can be dissolved in common solvent, so that the application range of the visible light responding TiO2 precursor is expanded, and the visible light responding TiO2 precursor can be used for preparing various products such as coatings, fibers and the like.
The invention also provides a visible light responding TiO2 catalyst.
Specifically, the TiO2 catalyst is obtained by cracking a visible light-responsive TiO2 precursor prepared by the preparation method of the invention at 350-500 ℃ in air.
Tests show that the TiO2 catalyst loaded by quartz fibers is repeatedly used for 10 times, and the degradation rate is not obviously changed.
Compared with the prior art, the invention has the following advantages:
In the prior art, a TiO2 photocatalyst generally exists in a powder form, a photocatalytic reaction is generally carried out in a suspended state photocatalytic reaction system, and the problems that TiO2 powder is easy to agglomerate, continuous separation, recovery and recycling of the catalyst are difficult to realize, and the like exist; related research on loading of powder is also carried out, but the problems of uneven loading and easy powder falling generally exist; moreover, the ordinary TiO2 catalyst only responds to ultraviolet light, and the ultraviolet light part in sunlight only accounts for less than 5%, so that the problem seriously limits the application of the TiO2 photocatalyst in practice. The precursor of the visible light response TiO2 photocatalyst is a high molecular organic compound and has the processing characteristics of organic high molecules, so that the precursor can be loaded on a fiber, a sheet or a porous material (such as a molecular sieve) and other substrates through simple impregnation, then the substrate loaded with the precursor is sintered at high temperature in the air, the precursor is inorganic and is converted into the visible light response TiO2 photocatalyst to be loaded on the substrate, and the problem of catalyst recovery and the problem of no response of a common TiO2 catalyst to visible light are solved. Meanwhile, the high molecular chain segment is introduced into the molecular structure of the precursor, and the high molecular chain segment is cracked in the inorganic process of the precursor, so that the obtained TiO2 photocatalyst has a porous structure, the specific surface area of the catalyst is increased, and the photodegradation efficiency is favorably improved. The method has the beneficial effects that a TiO2 precursor containing a high-molecular chain segment, boron and nitrogen in a molecular structure is prepared, the specific surface area of a product obtained after cracking of the precursor is as high as 220m2/g (the specific surface area of a product without organic high molecules is 100m2/g), the product has good photocatalytic capacity under ultraviolet light (30 min degradation rate of methyl orange reaches 100% under the irradiation of a 500W high-pressure mercury lamp), and the product has good photocatalytic capacity under visible light (4 h degradation rate of methyl orange is 87.1% under the irradiation of a 500W xenon lamp).
drawings
FIG. 1 is a graph of the degradation rate of a quartz fiber supported TiO2 catalyst after 10 cycles of reuse;
FIG. 2 is an XRD curve of the precursor after cracking at 450 ℃ in air.
Detailed Description
the following are specific embodiments of the present invention, which are intended to further illustrate the invention and not to limit it.
Example 1
In this embodiment, the visible light-responsive TiO2 precursor is synthesized by the following steps:
(1) Putting 1mol of tetrapropyl titanate and 143.7g of polyethylene glycol into a drying reaction kettle provided with a condensing tube and a drying tube, adding 0.3mol of boric acid under stirring at 50 ℃, and reacting at 100 ℃ until the system is clear and transparent;
(2) At room temperature, adding 0.1mol of ethanolamine into the system, and heating and refluxing for 0.5 h;
(3) Adjusting the temperature to room temperature, adding 1mol of acetylacetone, and heating and refluxing for 0.5 h;
(4) Adjusting the temperature to 80 ℃, dripping a mixed solution of 0.8mol of water and 2.5mol of n-propanol, refluxing for 1h after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
and cracking the obtained precursor at 500 ℃ in air to obtain the B and N codoped TiO2 catalyst.
30mg of the obtained catalyst is added into 30ml of methyl orange solution (the concentration is 15mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 65%.
Example 2
In this embodiment, the visible light-responsive TiO2 precursor is synthesized by the following steps:
(1) putting 1mol of tetraisopropyl titanate and 10g of polymethyl methacrylate into a drying reaction kettle provided with a condensing tube and a drying tube, adding 0.08mol of boric acid under stirring at 90 ℃, and reacting at 100 ℃ until the system is clear and transparent;
(2) At the temperature of 90 ℃, adding 0.3mol of ethanolamine into the system, and heating and refluxing for 1 h;
(3) adjusting the temperature to 100 ℃, adding 0.8mol of ethyl acetoacetate, and heating and refluxing for 1 h;
(4) And adjusting the temperature to room temperature, dripping a mixed solution of 1.2mol of water and 6mol of isopropanol, refluxing for 3 hours after dripping, and reducing the pressure and removing the solvent after cooling to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
and cracking the obtained precursor at 450 ℃ in air to obtain the B and N codoped TiO2 catalyst.
30mg of the obtained catalyst is added into 30ml of methyl orange solution (the concentration is 15mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 76.9 percent.
The precursor is dissolved in n-propanol to prepare a solution with the Ti content of 3%, 0.15g of quartz fiber is soaked, and then the quartz fiber-supported TiO2 catalyst is prepared by solidification and pyrolysis, wherein the catalyst loading rate is 20%. Adding the supported catalyst into 30ml of methyl orange solution (the concentration is 15mg/L), and irradiating for 30min by using a 500W high-pressure mercury lamp, wherein the degradation rate is 100%; when a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4h, the degradation rate is about 50%, as shown in figure 1, the fabric is repeatedly used for ten times, and the degradation rate is not obviously changed.
example 3
In this embodiment, the visible light-responsive TiO2 precursor is synthesized by the following steps:
(1) Placing 1mol of tetrabutyl titanate and 96g of polypropylene glycol into a drying reaction kettle equipped with a condensing tube and a drying tube, adding 0.24mol of boric acid under stirring at 70 ℃, and reacting at 100 ℃ until the system is clear and transparent;
(2) adding 2mol of acetamide into the system at 50 ℃, and heating and refluxing for 5 h;
(3) Adjusting the temperature to room temperature, adding 0.1mol of ethyl acetoacetate, and heating and refluxing for 5 h;
(4) adjusting the temperature to 80 ℃, dripping a mixed solution of 0.8mol of water and 2.5mol of n-butyl alcohol, refluxing for 8h after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
Cracking the obtained precursor at 400 ℃ in air to obtain B, N codoped TiO2 catalyst.
Adding 30mg of the obtained catalyst into 30ml of methyl orange solution (the concentration is 15mg/L), and irradiating for half an hour by using a 500W high-pressure mercury lamp, wherein the degradation rate is 100%; A500W xenon lamp (a filter plate filters light with the wavelength of less than 420 nm) is illuminated for 4 hours, and the degradation rate is 87.1 percent.
The XRD curve of the precursor after cracking at 400 ℃ in air is shown in figure 2, and the TiO2 catalyst obtained after cracking the precursor is anatase.
Example 4
In this embodiment, the visible light-responsive TiO2 precursor is synthesized by the following steps:
(1) Putting 1mol of tetraisobutyl titanate and 5g of polyvinylpyrrolidone into a drying reaction kettle provided with a condensing tube and a drying tube, adding 0.04mol of boric acid under stirring at 80 ℃, and reacting at 120 ℃ until the system is clear and transparent;
(2) Adding 2mol of glycine into the system at room temperature, and heating and refluxing for 2 h;
(3) Adjusting the temperature to 60 ℃, adding 0.6mol of acetylacetone, and heating and refluxing for 3 h;
(4) Adjusting the temperature to 40 ℃, dripping a mixed solution of 0.8mol of water and 2.5mol of n-propanol, refluxing for 5h after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
the precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
and cracking the obtained precursor at 400 ℃ in air to obtain the B and N codoped TiO2 catalyst.
30mg of the obtained catalyst is added into 30ml of methyl orange solution (the concentration is 20mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 82.2 percent.
example 5
in this embodiment, the visible light-responsive TiO2 precursor is synthesized by the following steps:
(1) Putting 1mol of tetraisopropyl titanate and 120g of polyethylene glycol into a drying reaction kettle equipped with a condensing tube and a drying tube, adding 0.2mol of boric acid under stirring at 50 ℃, and reacting at 120 ℃ until the system is clear and transparent;
(2) Adding 2mol of alanine into the system at room temperature, and heating and refluxing for 2 h;
(3) adjusting the temperature to 50 ℃, adding 0.6mol of acetylacetone, and heating and refluxing for 3 h;
(4) and adjusting the temperature to 75 ℃, dripping a mixed solution of 0.8mol of water and 2.4mol of isobutanol, refluxing for 5 hours after dripping, reducing the temperature, and removing the solvent to obtain the precursor.
the precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
And cracking the obtained precursor at 400 ℃ in air to obtain the B and N codoped TiO2 catalyst.
30mg of the obtained catalyst is added into 30ml of methyl orange solution (the concentration is 20mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 66%.
Example 6
In this embodiment, the visible light-responsive TiO2 precursor is synthesized by the following steps:
(1) Putting 1mol of tetraisopropyl titanate and 120g of polyethylene glycol into a drying reaction kettle equipped with a condensing tube and a drying tube, adding 0.16mol of boric acid under stirring at 50 ℃, and reacting at 110 ℃ until the system is clear and transparent;
(2) Adding 3mol of N, N-dimethylacetamide into the system at room temperature, and heating and refluxing for 2 h;
(3) Adjusting the temperature to 90 ℃, adding 0.6mol of acetylacetone, and heating and refluxing for 3 h;
(4) And adjusting the temperature to 70 ℃, dripping a mixed solution of 1.3mol of water and 26mol of ethanol, refluxing for 5 hours after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
the precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
And cracking the obtained precursor at 350 ℃ in air to obtain the B and N codoped TiO2 catalyst.
30mg of the obtained catalyst is added into 30ml of methyl orange solution (the concentration is 20mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 64.3 percent.
Claims (9)
1. A preparation method of a visible light response TiO2 precursor is characterized by comprising the following steps:
1) Placing titanate and organic polymer in a reaction container, adding boric acid at 50-90 ℃, and reacting at 100-120 ℃ until the solution is clear and transparent;
2) adding a nitrogen-containing compound at room temperature to 90 ℃, and heating and refluxing;
3) Adding a chelating agent at room temperature to 100 ℃, and heating and refluxing;
4) dripping mixed solution of water and alcohol at room temperature to 80 ℃, refluxing after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the visible light response TiO2 precursor;
The mass of the organic polymer is 0.1-3 times of the mass of Ti atoms in the system, and the organic polymer is one or a mixture of polyethylene glycol, polypropylene glycol, polymethyl methacrylate and polyvinylpyrrolidone.
2. the preparation method according to claim 1, wherein the molar ratio of the boric acid to the titanate is (0.04-0.3): 1.
3. The process according to claim 1 or 2, wherein the molar ratio of the titanate, the nitrogen-containing compound, the chelating agent and the water is 1: (0.1-3): (0.1-1): (0.8 to 1.3).
4. The method according to claim 3, wherein the molar ratio of water to alcohol in the mixed solution of water and alcohol is 1: (3-20).
5. the preparation method according to claim 1, wherein the heating reflux time in the step 2) is 0.5-5 h;
The heating reflux time in the step 3) is 0.5-5 h;
And 4) refluxing for 1-8 h.
6. the preparation method according to claim 5, wherein in step 1), the titanate is one or a mixture of more of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate or tetraisobutyl titanate;
In the step 2), the nitrogen-containing compound is one or a mixture of more of ethanolamine, acetamide, N-dimethylacetamide, glycine or alanine;
in the step 3), the chelating agent is one or a mixture of acetylacetone and ethyl acetoacetate;
in the step 4), in the mixed solution of water and alcohol, the alcohol is one or a mixture of ethanol, n-propanol, isopropanol, n-butanol or isobutanol.
7. The method according to claim 6, wherein the nitrogen-containing compound is ethanolamine, acetamide or N, N-dimethylacetamide.
8. A visible light-responsive TiO2 precursor, characterized in that, the visible light-responsive TiO2 precursor prepared by the preparation method according to any one of claims 1 to 7 is dissolved in any one solvent or a mixed solvent of several solvents of ethanol, n-propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
9. the visible-light-responsive TiO2 catalyst is characterized in that the visible-light-responsive TiO2 catalyst is obtained by cracking the visible-light-responsive TiO2 precursor prepared by the preparation method of any one of claims 1 to 7 at 350-500 ℃ in air.
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