CN111921515A - Fibrous double-crystal-phase titanium dioxide and preparation method and application thereof - Google Patents
Fibrous double-crystal-phase titanium dioxide and preparation method and application thereof 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 169
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- GHDSNRQFECQVII-UHFFFAOYSA-N [Ti].OOO Chemical compound [Ti].OOO GHDSNRQFECQVII-UHFFFAOYSA-N 0.000 claims description 11
- 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 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000002121 nanofiber Substances 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- -1 etc. Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003075 TiO2-B Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910003083 TiO6 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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Abstract
The invention discloses a fibrous double-crystal phase titanium dioxide and a preparation method thereof, wherein the fibrous double-crystal phase titanium dioxide comprises anatase phase titanium dioxide and TiO phase titanium dioxide2-phase B, said bi-crystalline phase titanium dioxide being in the form of nanofibres. The fibrous double-crystal phase titanium dioxide has the advantages of novel structure, large length-diameter ratio, good appearance and size uniformity, and is expected to be further applied in the field of photocatalysis and other fields.
Description
Technical Field
The invention relates to the technical field of inorganic nano materials, in particular to fibrous double-crystal-phase titanium dioxide, a preparation method thereof and application thereof in the field of photocatalysis.
Background
With the continuous development of industrialization, the problems of energy shortage and environmental pollution faced by human society are becoming more and more serious, and the energy system based on fossil fuel in the past can not meet the new requirements of people on energy source for long time, high efficiency, cleanness, safety and economy, so scientists put more energy into photolysis water to produce hydrogen and CO2The curing and converting research fields and the like find a solution for the global energy and environmental pollution problems. In the field of photocatalysis, the development of various novel catalyst materials is an important part, and TiO2The material is a common industrial grade photocatalytic material due to its very stable chemical properties, low price and suitable catalytic activity. Thus, TiO enhancement2The photocatalytic performance of the material has important significance for the development of photocatalytic technology.
TiO2The crystal forms of the crystal forms include rutile, anatase, brookite and monoclinic phase TiO2-B, etc., TiO2B is a mixture of edge-sharing and corner-sharing TiO6Octahedral, which is an open framework structure of relatively low density, is composed of a large number of unoccupied stacks of vacancy octahedral units having lattice parameters a-12.1787, b-3.7412,
beta is 107.054 degrees, belonging to C2/m space group. TiO 22the-B is an n-type semiconductor, has a band gap of 3-3.22 eV, has unique catalytic characteristics and thermal stability, is a catalytic carrier with high activity and selectivity, and has certain performance in the aspects of photocatalytic water decomposition for hydrogen production and organic pollutant degradation.
But single phase TiO2B has higher photoproduction electron-hole recombination rate by combining anatase phase titanium dioxide with TiO2And (4) the-B is compounded, so that two phases form a heterojunction, the separation of photogenerated electrons and holes can be promoted, and the photocatalytic performance of the material is improved. The photocatalytic performance of the composite structures with different morphologies also differs, so that the development of the composite structures with different morphologies is necessary.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses fibrous bicrystal phase titanium dioxide and a preparation method thereof, wherein the fibrous bicrystal phase titanium dioxide with a novel structure is prepared by two hydrothermal reactions, and is expected to be further applied in the field of photocatalysis and other fields.
The specific technical scheme is as follows:
a fibrous double-crystal phase titanium dioxide comprises anatase phase titanium dioxide and TiO2-phase B, said bi-crystalline phase titanium dioxide being in the form of nanofibres.
Preferably:
the diameter of the bi-crystal phase titanium dioxide is 20-50 nm, and the length of the bi-crystal phase titanium dioxide is 400-1000 nm.
Preferably:
the anatase/TiO2In the B double-crystal-phase nano fiber, the mass percentage of anatase phase titanium dioxide is 20-35%; more preferably 25 to 30%.
Further preferably, the diameter of the bi-crystal phase titanium dioxide is 20-30 nm, and the length of the bi-crystal phase titanium dioxide is 800-1000 nm.
The invention also discloses a preparation method of the fibrous double-crystal-phase titanium dioxide, which comprises the following steps:
(1) hydrolyzing tetrabutyl titanate to obtain titanium oxyhydroxide precipitate;
(2) dispersing titanium oxyhydroxide precipitate in water, adding potassium hydroxide, and performing hydrothermal reaction to obtain potassium titanate fiber;
(3) and (3) dispersing the potassium titanate fiber prepared in the step (2) in an ethanol-water mixed system, adding hydrochloric acid, and carrying out secondary hydrothermal reaction to obtain the fibrous double-crystal-phase titanium dioxide.
The fibrous double-crystal-phase titanium dioxide is prepared by two hydrothermal reactions and simultaneously contains anatase phase and TiO phase2Phase B, a mixed crystal form of titanium dioxide. The double-crystal phase titanium dioxide is in a nano-fiber shape, and the anatase phase and the TiO phase2the-B phase forms a heterojunction structure.
In the step (1), the hydrolysis reaction specifically comprises:
dissolving tetrabutyl titanate in ethanol, slowly adding water, and hydrolyzing to obtain titanium oxyhydroxide precipitate Ti (OH)4。
Preferably, the molar concentration of the tetrabutyl titanate in the ethanol is 0.2-0.35 mol/L, and more preferably 0.27-0.3 mol/L.
In the step (2):
preferably, the mass volume ratio of the titanium oxyhydroxide precipitate to water is 0.016-0.03 g/mL; more preferably 0.02 to 0.025 g/mL.
Preferably, the molar ratio of tetrabutyl titanate to potassium hydroxide is 1: 40-60; more preferably 1: 45-50.
Preferably, the temperature of the hydrothermal reaction is 180-220 ℃; further preferably 190-210 ℃, and the reaction time is 1-24 h.
The chemical formula of the prepared potassium titanate fiber is K through XRD characterization2Ti6O13。
In the step (3):
the double-crystal-phase titanium dioxide prepared by adopting an ethanol-water system is in a nano-fiber shape, uniform in size and good in dispersity. Tests show that the appearance of the prepared product can be changed when different organic solvents are adopted.
Under the preparation process, the volume fraction of ethanol in an ethanol-water mixed system has important influence on the morphology of the prepared double-crystal-phase titanium dioxide. Preferably, in the ethanol-water mixed system, the volume fraction of ethanol is 50-87.5%; more preferably, the volume fraction of ethanol is 75%. Tests show that when the volume fraction of ethanol is 50-87.5%, the prepared double-crystal-phase titanium dioxide is in a nano-fiber shape, but when the volume fraction of ethanol is 75%, the prepared double-crystal-phase titanium dioxide fiber is larger in length-diameter ratio and narrower in length and diameter distribution, namely, the size of the fiber is more uniform.
Preferably:
in the ethanol-water mixed system, the concentration of the potassium titanate fiber is 0.007-0.008 g/mL; further preferably 0.0075 g/mL.
Preferably, the temperature of the secondary hydrothermal reaction is 180-220 ℃, and the time is 1-36 h. More preferably, the time of the secondary hydrothermal reaction is 10-36 h.
In step (3), the choice of hydrochloric acid is also of critical importance, and tests show that under the same process conditions, if hydrochloric acid is replaced by other acids common in the field, the prepared product is not in a nano-fibrous state.
Preferably, the ratio of the amount of Ti to Cl in the potassium titanate fibers to the amount of hydrochloric acid is 1: 1-5, feeding; more preferably, the ratio of the amount of Ti to Cl in the potassium titanate fibers to the amount of hydrochloric acid is 1: 1.5-1.8, and feeding. More preferably, the ratio of the amount of Ti to Cl is 1:1.5, tests show that the fibrous double-crystal-phase titanium dioxide prepared by the feeding ratio has more uniform appearance.
Further preferably:
in the step (2),
the mass volume ratio of the titanium oxyhydroxide precipitate to water is 0.022 g/mL; the molar ratio of tetrabutyl titanate to potassium hydroxide is 1: 46.875;
in the step (3):
in the ethanol-water mixed system, the volume fraction of ethanol is 75 percent;
in the ethanol-water mixed system, the concentration of the potassium titanate fiber is 0.0075 g/mL;
the ratio of the amount of Ti to Cl substances in the potassium titanate fiber to the amount of hydrochloric acid is 1:1.5, feeding; the hydrothermal reaction was carried out at 200 ℃ for 30 h.
Tests show that under the preferable process parameters, the prepared fibrous double-crystal phase titanium dioxide has more uniform appearance, larger length-diameter ratio and more uniform size.
The invention also discloses application of the fibrous double-crystal-phase titanium dioxide in the field of photocatalysis.
Compared with the prior art, the invention has the following advantages:
the invention prepares a shape by a two-step hydrothermal methodNovel-looking bicrystal phase titanium dioxide, and anatase phase and TiO phase in the product2The phase B is titanium dioxide in a mixed crystal form, is in a nano fiber shape, has a large length-diameter ratio and is uniform in size.
Drawings
FIG. 1 is an SEM image of an intermediate potassium titanate prepared in example 1;
FIG. 2 is an XRD pattern of the intermediate potassium titanate prepared in example 1;
FIG. 3 is an XRD pattern of the fibrous, two-crystal phase titanium dioxide prepared in example 1;
FIG. 4 is an SEM image of the fibrous twinned phase titanium dioxide prepared in example 1;
FIG. 5 is an SEM image of the fibrous twinned phase titanium dioxide prepared in example 2;
FIG. 6 is an SEM image of the fibrous twinned phase titanium dioxide prepared in example 3;
FIG. 7 is an SEM image of the fibrous twinned phase titanium dioxide prepared in example 4;
FIG. 8 is an XRD pattern of the product prepared in comparative example 1;
fig. 9 is an SEM image of the product prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto.
Example 1
1) 2mL (5.76X 10)-3mol) tetrabutyl titanate is dissolved in 20mL absolute ethyl alcohol, stirred for 5min to be uniform, deionized water is slowly dripped by a dropper to obtain white precipitate, and titanium oxyhydroxide precipitate is obtained by centrifugation and washing.
2) 0.667g of titanium oxyhydroxide precipitate was dispersed in 30mL of deionized water, stirred for 10min to homogenize, 18g of potassium hydroxide (0.27mol) was added, and deionized water was added to make a volume of 40mL, at which time the concentration of potassium hydroxide was 6.8 mol/L. And transferring the suspension into a polytetrafluoroethylene reaction kettle with the volume of 50mL, carrying out hydrothermal reaction for 16h at the temperature of 200 ℃, cooling at room temperature, washing the product with dilute nitric acid, deionized water and absolute ethyl alcohol respectively to obtain an intermediate product potassium titanate, and drying in an oven at the temperature of 70 ℃.
3) 0.3g (5.23X 10) of dried potassium titanate fiber was weighed-4mol) is dispersed in 30mL ethanol, deionized water is added to the mixture until the volume is 40mL, the volume fraction of the ethanol in the mixed system is 75 percent, 385 mu L and 38wt percent hydrochloric acid (4.775 multiplied by 10) are added- 3mol) and stirring for 30min to mix evenly. At this time, the ratio of the amount of Ti to Cl was about 1:1.5, and the molar concentration of hydrochloric acid in the mixed system was 0.11 mol/L. And transferring the suspension into a polytetrafluoroethylene reaction kettle with the volume of 50mL, carrying out hydrothermal reaction at 200 ℃ for 30h, cooling at room temperature, and washing with deionized water and absolute ethyl alcohol respectively to obtain the fibrous double-crystal-phase titanium dioxide.
SEM and XRD characterization is carried out on the intermediate product potassium titanate, and the morphology is fibrous as shown in figures 1 and 2 respectively.
XRD characterization was performed on the product, and as shown in FIG. 3, diffraction peak energy in XRD pattern is indexed to anatase TiO2And monoclinic phase TiO2B, which is consistent with the reports of PDF #21-1272 and #74-1940, indicating that the product is anatase/TiO2And the mass percent of anatase phase titanium dioxide in the product is 26 percent through full peak fitting calculation.
Aiming at SEM representation, as shown in figure 4, the fibrous double-crystal-phase titanium dioxide prepared under the concentration has the diameter of 20-30 nm, the length of 800-1000 nm, uniform appearance and size, large length-diameter ratio and good dispersibility.
Example 2
The preparation process is basically the same as that in example 1, except that, in step 3), 35mL of ethanol is used, water is added to the mixture to make the volume of the mixture reach 40mL, and the volume fraction of the ethanol in the mixture system is 87.5%.
XRD characterization of the product was performed, and the product obtained in this example was also anatase/TiO2the-B double-crystal-phase nano fiber contains 29% of anatase-phase titanium dioxide by mass.
The SEM representation is shown in figure 5, the fibrous double-crystal-phase titanium dioxide prepared under the concentration has the diameter of 20-50 nm, the length of 200-500 nm, the length-diameter ratio smaller than that of the product prepared in example 1, the appearance is uniform, the size uniformity is slightly worse than that of example 1, and the dispersibility is good.
Example 3
The preparation process is basically the same as that in example 1, except that in step 3), 20mL of ethanol is used, water is added to the mixture to make the volume of the mixture reach 40mL, and the volume fraction of the ethanol in the mixed system is 50%.
XRD characterization of the product was performed, and the product obtained in this example was also anatase/TiO2the-B double-crystal-phase nano-fiber contains 25 percent of anatase-phase titanium dioxide by mass.
The SEM representation is shown in figure 6, the fibrous double-crystal-phase titanium dioxide prepared under the concentration has the diameter of 20-30 nm, the length of 400-1000 nm, uniform appearance, slightly worse size uniformity than that of example 1 and good dispersibility.
Example 4
The preparation process was substantially the same as in example 1, except that, in step 3), the amount of 38% by weight hydrochloric acid used was 470. mu.L (5.613X 10)-3mol) the amount of Ti to Cl species at this time was about 1:1.76, and the molar concentration of hydrochloric acid in the mixed system was 0.134 mol/L.
XRD characterization is carried out on the product, and diffraction peak energy in an XRD pattern is indexed to anatase type TiO2And monoclinic phase TiO2B, which is consistent with the reports of PDF #21-1272 and #74-1940, indicating that the product is anatase/TiO2-B a double crystalline phase, the mass percentage of anatase phase titanium dioxide being 34%.
The SEM representation is shown in figure 7, and the fibrous double-crystal-phase titanium dioxide prepared under the concentration has the diameter of 20-30 nm, the length of 200-1000 nm and slightly poor size uniformity; other products with different shapes appear in the product, and the shape uniformity is also slightly poor.
Comparative example 1
The preparation process is basically the same as that in example 1, except that in the process of preparing the fibrous twinned phase titanium dioxide in step 3), ethanol is not added, and only deionized water is added to a constant volume of 40 mL.
XRD and SEM characterization is carried out on the product, under the condition that only deionized water is added as a solvent,the XRD pattern is shown in FIG. 8, in which all diffraction peaks can only be indexed to TiO2-phase B TiO2This is consistent with that reported in PDF #74-1940, indicating that the product is TiO2-phase B TiO2。
The SEM representation of the product is shown in FIG. 9, the diameter of the nanofiber is 25-35 nm, and the length of the nanofiber is 200-500 nm.
Comparative example 2
The preparation process is basically the same as that in example 1, except that in the process of preparing the fibrous double-crystal phase titanium dioxide in the step 3), the used organic solvent is ethylene glycol, 30mL of the used ethylene glycol is added with water to a constant volume of 40mL, and the volume fraction of the ethanol in the mixed system is 75%.
XRD characterization is carried out on the product, and under the condition that the volume fraction of the glycol is 75%, the XRD pattern of the product is shown in figure 2, wherein all diffraction peaks can only be indexed to potassium titanate K2Ti6O13It is stated that when ethylene glycol is used as a solvent in an amount of 75% by volume, fibrous twinned phase titanium dioxide cannot be obtained.
Claims (10)
1. A fibrous double-crystal phase titanium dioxide is characterized by comprising anatase phase titanium dioxide and TiO2-phase B, said bi-crystalline phase titanium dioxide being in the form of nanofibres.
2. The fibrous two-crystal phase titanium dioxide according to claim 1, wherein the diameter of the two-crystal phase titanium dioxide is 20 to 50nm and the length thereof is 400 to 1000 nm.
3. The fibrous twinned phase titanium dioxide of claim 1, wherein the mass percent of anatase phase titanium dioxide in the fibrous twinned phase titanium dioxide is 20-35%.
4. A method for producing fibrous twin-phase titanium dioxide according to any one of claims 1 to 3, comprising the steps of:
(1) hydrolyzing tetrabutyl titanate to obtain titanium oxyhydroxide precipitate;
(2) dispersing titanium oxyhydroxide precipitate in water, adding potassium hydroxide, and performing hydrothermal reaction to obtain potassium titanate fiber;
(3) and (3) dispersing the potassium titanate fiber prepared in the step (2) in an ethanol-water mixed system, adding hydrochloric acid, and carrying out secondary hydrothermal reaction to obtain the fibrous double-crystal-phase titanium dioxide.
5. The method for producing fibrous twin-phase titanium dioxide according to claim 4, wherein in the step (2):
the mass volume ratio of the titanium oxyhydroxide precipitate to water is 0.016-0.03 g/mL;
the molar ratio of tetrabutyl titanate to potassium hydroxide is 1: 40-60;
the temperature of the hydrothermal reaction is 180-220 ℃.
6. The method for producing fibrous twin-phase titanium dioxide according to claim 4, wherein in the step (3):
in the ethanol-water mixed system, the volume fraction of ethanol is 50-87.5%;
in the ethanol-water mixed system, the concentration of the potassium titanate fiber is 0.007-0.008 g/mL;
the temperature of the secondary hydrothermal reaction is 180-220 ℃, and the time is 1-36 h.
7. The method for producing fibrous twin-phase titanium dioxide according to claim 4, wherein in the step (3):
the ratio of the amount of Ti to Cl substances in the potassium titanate fiber to the amount of hydrochloric acid is 1: and (1) feeding materials to 5.
8. The method for producing fibrous twin-phase titanium dioxide according to claim 7, wherein the ratio of the amount of Ti to Cl substance between the potassium titanate fibers and the hydrochloric acid is 1: 1.5-1.8, and feeding.
9. The method for producing fibrous twin-phase titanium dioxide according to any one of claims 4 to 8, wherein:
in the step (2),
the mass volume ratio of the titanium oxyhydroxide precipitate to water is 0.022 g/mL; the molar ratio of tetrabutyl titanate to potassium hydroxide is 1: 46.875;
in the step (3):
in the ethanol-water mixed system, the volume fraction of ethanol is 75 percent;
in the ethanol-water mixed system, the concentration of the potassium titanate fiber is 0.0075 g/mL;
the ratio of the amount of Ti to Cl substances in the potassium titanate fiber to the amount of hydrochloric acid is 1:1.5, feeding; the hydrothermal reaction was carried out at 200 ℃ for 30 h.
10. Use of the fibrous twinned phase titanium dioxide according to any of claims 1-3 in the field of photocatalysis.
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