WO2014117487A1 - Graded mixed crystal tio2 micro/nano material, preparation method therefor and application thereof - Google Patents

Graded mixed crystal tio2 micro/nano material, preparation method therefor and application thereof Download PDF

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WO2014117487A1
WO2014117487A1 PCT/CN2013/080138 CN2013080138W WO2014117487A1 WO 2014117487 A1 WO2014117487 A1 WO 2014117487A1 CN 2013080138 W CN2013080138 W CN 2013080138W WO 2014117487 A1 WO2014117487 A1 WO 2014117487A1
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micro
mixed crystal
nano material
further preferably
aqueous solution
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French (fr)
Chinese (zh)
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朴玲钰
解英娟
吴志娇
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国家纳米科学中心
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the invention relates to a graded mixed crystal 10 2 micro-nano material, a preparation method and the use thereof, in particular to a graded mixed crystal Ti0 2 assembled by a one-dimensional nanowire and having a crystal form of an anatase and rutile mixed crystal form.
  • the formed heterojunction structure increases the number of traps capable of trapping electrons and holes in the system, and can effectively separate photogenerated electron-hole pairs, thereby improving photocatalytic activity.
  • the above phenomenon is also called mixed crystal effect.
  • the graded 02 micro-nano material has a nano-scale structure, shortens the migration time of photogenerated electrons and holes, and effectively increases the separation rate, thereby improving the photocatalytic activity of the material; another property advantage brought by the nano-scale structure is High specific surface area. High specific surface area increases the contact area of the photocatalytic reaction, thus improving the photocatalytic activity of a material; micron-scale structures 102 such that during use to maintain structural stability, which is the catalytic The performance that the agent must have to use.
  • the invention uses a sol-gel method and a hydrothermal method to prepare a graded mixed crystal 0 2 micro-nano material with novel morphology and excellent performance.
  • One of the objects of the present invention is to provide a graded mixed crystal 02 micro/nano material with novel morphology and excellent performance, and the graded mixed crystal 10 2 micro-nano material is a graded flower-like structure, a mixed crystal phase, and has excellent properties. Photocatalytic activity and structural stability.
  • a graded mixed crystal 1 0 2 micro-nano material wherein the micro-nano material is a flower-like structure formed by assembling nanowires, the diameter of the flower-like structure is 2 ⁇ 4 ⁇ , the diameter of the nanowire is 10-30 nm, and the length of the nanowire It is 0.9 ⁇ 2 ⁇ , and the crystal form is anatase-rutile mixed crystal.
  • the upper and lower surfaces of the flower-like structure can be fully utilized to improve the catalytic activity and structural stability of the 2 micro-nano material as a catalyst.
  • the anatase-rutile mixed crystal effect also enhances the catalytic activity of the graded mixed crystal 02 micro-nanomaterial as a catalyst.
  • the invention combines the flower-like hierarchical micro-nano structure with the anatase-rutile mixed crystal to obtain a graded mixed crystal 10 2 micro-nano material which is excellent in catalytic activity and structural stability.
  • the flower-like structure has a diameter of 2.2 to 3.6 ⁇ m, such as 2.4 ⁇ m, 2.1 ⁇ m, 2.5 ⁇ m, 2.7 ⁇ m, 2.9 ⁇ m, 3.1 ⁇ m, 3.4 ⁇ m, 3.3 ⁇ m, 3.6 ⁇ m, 3.9 ⁇ m, preferably 2.4 3.4 ⁇ m.
  • the nanowires have a diameter of 12 to 28 nm, such as 11 ⁇ , 13 ⁇ , 16 ⁇ , 18 ⁇ , 20 ⁇ , 22 ⁇ , 24 nm, 26 nm, 28 nm, 29 nm, preferably 14 to 27 nm.
  • the nanowires have a length of 1.1 to 1.9 ⁇ m, such as 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m, preferably 1.15 to 1.85 ⁇ m.
  • the mass percentage of the rutile phase is 50 to 60%, for example, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59% 59.5%, preferably 52 ⁇ 58%, and further preferably 53 ⁇ 57%.
  • a second object of the present invention is to provide a method for preparing a graded mixed crystal 02 micro-nano material as described above, which is prepared by a sol-gel method and a hydrothermal method to prepare a flower-like structure having a nanowire as a basic structure.
  • Graded mixed crystal Ti0 2 micro-nano materials The flower-like structure has a diameter of 2 to 4 ⁇ , a one-dimensional nanowire having a diameter of 10 to 30 nm, a nanowire length of 0.9 to 2 ⁇ , and a crystal form of an anatase-rutile mixed crystal.
  • the organic compound of titanium is selected from any one or a mixture of at least two of tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate, such as tetrabutyl titanate and titanic acid.
  • tetraisopropyl ester a mixture of tetraethyl titanate and tetrabutyl titanate, a mixture of tetraisopropyl titanate and tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate and titanium
  • a mixture of tetraethyl acid preferably tetrabutyl titanate and/or tetraisopropyl titanate, further preferably tetrabutyl titanate.
  • the concentration of the titanium organic compound in the aqueous alcohol solution is 0.01 to 0.1 mol/L, for example, 0.02 mol/L, 0.03 mol/L, 0.04 mol/L, 0.05 mol/L, 0.06 mol/L, and 0.07 mol/L. , 0.08mol/L, 0.09 mol/L, preferably 0.015 to 0.095 mol/L, and further preferably 0.025 to 0.085 mol/L.
  • the alcohol is selected from any one of ethanol, propanol or butanol or a mixture of at least two, preferably ethanol.
  • the aqueous alcohol solution is a solution of ethanol and water, and the volume ratio of the ethanol to water is 15:1 to 1:15, for example, 14:1, 10:1, 1:1, 1:5, 1: 10, 1 : 14, preferably 10:1 1 : 10, further preferably 5:1 to 1:5.
  • the standing time is 10-15 h, for example 10.2 h, 10.5 h, 10.9 h, 11.3 h, 11.6 h, 12.2 h, 12.8 h, 13.4 h, 13.9 h, 14.3 h, 14.8 h, preferably 10.5 to 14.5 h. , a further preferred ll ⁇ 14h.
  • the condensing reflux is carried out in an oil bath having a temperature of 100 200 ° C, for example 110 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C 180 ° C, 190 ° C, preferably 105 ⁇ 195 ° C, further preferably 115 ⁇ 185 ° C.
  • the condensing reflux time is 20 ⁇ 40h, for example 21h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, preferably 22 ⁇ 39h, and further preferably 25 ⁇ 35h.
  • the sol obtained in the step (1) is condensed and refluxed with hydrochloric acid, and the addition of hydrochloric acid causes formation of an anatase-rutile mixed crystal.
  • the molar ratio of the hydrochloric acid to the titanium ion is 5:1 to 15:1, for example, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1 14:1, preferably 5.5:1 ⁇ 14.5:1, further preferably 6.5:1 13.5:1.
  • Step (3) Wash the precipitate with ethanol and deionized water.
  • the calcination temperature in the step (3) is 200 400 ° C, for example, 210 ° C, 230 ° C, 250. C, 270. C, 290 ° C, 310 ° C, 330 ° C, 350 ° C, 370 ° C, 390 ° C, preferably 220 380 ° C, further preferably 240 ⁇ 260.
  • the concentration of the aqueous NaOH solution is 5 to 10 mol/L, for example, 5.5 mol/L, 6 mol/L, 6.5 mol/L, 7 mol/L, 7.5 mol/L, 8 mol/L, 8.5 mol/L, and 9 mol. /L, 9.5mol/L, preferred 5.8 ⁇ 9.8mol/L, further 6.3 ⁇ 9.2mol/L.
  • the white powder was reacted with an aqueous NaOH solution to obtain a hierarchical structure of a 10 2 micronanometer material.
  • the volume of the aqueous NaOH solution is 30 to 70 mL, for example, 34 mL, 38 mL, 42 mL, 46 mL, 51 mL, 55 mL, 59 mL, 63 mL, 67 mL, preferably 35 to 65 mL, and further preferably 40 to 60 mL.
  • the temperature of the reaction described in the step (4) is from 120 to 200. C, for example 130. C, 140. C, 150. C, 160. C, 170 ° C, 180 ° C, 190 ° C, preferably 125 to 195 ° C, further preferably 135 to 185 ° C.
  • the reaction time of the step (4) is 3 ⁇ 5h, for example 3.2h, 3.4h, 3.6h, 3.8h, 4.1h, 4.3h, 4.6h, 4.8h, preferably 3.1 ⁇ 4.9h, further preferably 3.3 ⁇ 4.7h.
  • Step (5) Wash to a pH of 6.5 to 7.5, such as 6.55, 6.65, 6.75, 6.8, 6.9, 7, 7.1, 7.2, preferably 6.6 to 7.4, and further preferably 6.7 to 7.3.
  • Step (5) The separation is selected from any one selected from the group consisting of filtration, centrifugation, precipitation, gravity sedimentation or centrifugal sedimentation, preferably filtration or centrifugation, followed by centrifugation.
  • ( ⁇ ) tetrabutyl titanate is added dropwise to 100 ⁇ 200mL ethanol solution, the concentration of tetrabutyl titanate in ethanol aqueous solution is 0.01 ⁇ 0.1mol/L, and the volume ratio of ethanol to water is 1:15 ⁇ 15 : 1, after mixing evenly, after standing for 10 ⁇ 15h, the sol is obtained;
  • the present invention has the following beneficial effects:
  • the graded mixed crystal 1 0 2 micro-nano material of the present invention combines the advantages of flower-like hierarchical nanostructures and mixed crystals, and has excellent catalytic activity and structural stability;
  • the graded mixed crystal obtained by the method of the invention 2 micro-nano material has good dispersibility, high product purity, and the preparation method is environmentally friendly, the reaction condition is mild, the energy consumption is low, and the material has high photocatalytic activity and stability. Sexual, easy to promote;
  • Example 1 is a high-magnification SEM image of the Ti0 2 material prepared in Example 1;
  • Example 2 is an SEM image of the ⁇ 0 2 material obtained in Example 1;
  • Example 3 is an XRD pattern of the ⁇ 0 2 material prepared in Example 1;
  • Example 4 is a comparison diagram of photocatalytic effects of the ruthenium 2 material prepared in Example 1 and the commercial yttrium 25 degraded methylene blue solution;
  • Figure 5 is an SEM image of the ⁇ 0 2 material obtained in Example 2 ;
  • Fig. 6 is an XRD chart of the ⁇ 0 2 material obtained in Example 2 .
  • step (1) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 100 ° C for 22 hours to obtain a white emulsion;
  • Figure 1 and Figure 2 show the SEM images of the graded mixed crystal Ti0 2 micro/nano materials prepared in Example 1 at different magnifications. It can be seen from the figure that the diameter of the flower-like microspheres is about 3 ⁇ m, from nanometers.
  • the line element is composed of a structure having a diameter of about 20 nm and a length of about 1 ⁇ m.
  • 3 is an XRD pattern of the graded mixed crystal ⁇ 0 2 micro-nano material prepared in the present embodiment, which indicates that the obtained three-dimensional flower-like ⁇ 2 material has both a crystal structure of anatase and rutile, namely anatase- A rutile type mixed crystal in which the rutile phase content is 51.4%.
  • Degussa P25 nano-Ti0 2 is a mixed mixed crystal ⁇ 2 2 micro-nano material prepared in the present embodiment and the same mass of Degussa P25 nano-Ti0 2 is added to the same concentration of the same volume of methylene blue solution, and stirred under dark conditions for 1 hour to reach the adsorption-desorption equilibrium.
  • the change in the concentration of methylene blue solution over time under UV light showed a higher photocatalytic performance than Degussa P25.
  • step (1) The sol of step (1) is condensed and refluxed with 0.5 mol/L hydrochloric acid in an oil bath at 100 ° C for 22 hours to obtain a white emulsion;
  • FIG. 5 is a SEM image of the graded mixed crystal TiO 2 micro/nano material prepared in Example 2.
  • the flower microsphere has a diameter of about 2.5 ⁇ m, and is composed of a nanowire primitive structure.
  • the nanowires have a diameter of about 25 nm and a length of about 900 nm.
  • 6 is an XRD pattern of the graded mixed crystal Ti0 2 micro/nano material prepared in the present embodiment, which indicates that the obtained three-dimensional flower-like 110 2 material has a crystal structure of anatase and rutile, that is, anatase-rutile.
  • the mixed crystal, wherein the rutile phase content is 57.3%.
  • step (1) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 100 ° C for 24 hours to obtain a white emulsion;
  • the SEM image shows that the flower-like microspheres have a diameter of about 3 ⁇ m, and are composed of nanowire motifs.
  • the nanowires have a diameter of about 15 nm and a length of about 1.2 ⁇ m.
  • the XRD pattern shows that the three-dimensional flower-like ⁇ 0 2 material has a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 54.3%.
  • step (1) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 110 ° C for 24 hours to obtain a white emulsion;
  • the SEM image shows that the flower-like microspheres have a diameter of about 3.5 ⁇ m and are composed of a nanowire matrix structure having a nanowire diameter of about 30 nm and a length of about 1.5 ⁇ m.
  • the XRD pattern shows that the three-dimensional flower-like Ti0 2 material has both a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 52%.
  • step (1) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 100 ° C for 24 hours to obtain a white emulsion;
  • the SEM image shows that the flower-like microspheres have a diameter of about 3 ⁇ m and consist of a nanowire matrix structure having a diameter of about 25 nm and a length of about 1 ⁇ m.
  • the XRD pattern shows that the three-dimensional flower-like ⁇ 0 2 material has a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 53.5%.
  • the sol of the step (1) is condensed and refluxed with 0.05 mol/L hydrochloric acid in an oil bath at 200 ° C for 20 hours to obtain a white emulsion;
  • the SEM image shows that the flower-like microspheres have a diameter of about 2 ⁇ m and consist of a nanowire matrix structure having a diameter of about 10 nm and a length of about 1 ⁇ m.
  • the XRD pattern shows that the three-dimensional flower-like ⁇ 0 2 material has a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 50.2%.
  • O.lmol/L tetrabutyl titanate was added dropwise to a mixed solution of 10 mL of ethanol and 150 mL of water, mixed uniformly, and allowed to stand for 12 hours to obtain a sol;
  • step (1) The sol of step (1) is condensed and refluxed with 1.5 mol/L hydrochloric acid in an oil bath at 100 ° C for 40 hours to obtain a white emulsion;
  • the SEM image shows that the flower-like microspheres have a diameter of about 4 ⁇ m, and are composed of a nanowire matrix structure.
  • the nanowires have a diameter of about 20 nm and a length of about 2 ⁇ m.
  • the XRD pattern shows that the three-dimensional flower-like Ti0 2 material has both the anatase and rutile crystal structure, that is, an anatase-rutile mixed crystal, among which, rutile

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Abstract

Provided are a graded mixed crystal TiO2 micro/nano material, preparation method therefor and application thereof. By combining a sol-gel method and a hydrothermal method, a flower-shaped graded mixed crystal TiO2 micro/nano material with nanowires as base structure is prepared. The diameter of the flower-shaped structure is 2-4 μm; the diameter of the nanowires is 10-30 nm; the length of the nanowires is 0.9-2 μm; and the crystal structure is anatase-rutile mixed crystal. The TiO2 micro/nano material can be used in the field of photocatalysis.

Description

一种分级混晶 ΉΟ2微纳米材料、 制备方法及其用途 技术领域 Graded mixed crystal ΉΟ 2 micro nano material, preparation method and use thereof
本发明涉及一种分级混晶 1 02微纳米材料、 制备方法及其用途， 特别涉及 一种由一维纳米线组装的， 晶型为锐钛矿和金红石混合晶型的分级混晶 Ti02微 纳米材料、 制备方法， 以及其在光催化领域的用途。 The invention relates to a graded mixed crystal 10 2 micro-nano material, a preparation method and the use thereof, in particular to a graded mixed crystal Ti0 2 assembled by a one-dimensional nanowire and having a crystal form of an anatase and rutile mixed crystal form. Micro-nano materials, methods of preparation, and their use in the field of photocatalysis.
背景技术Background technique
02半导体材料由于具有良好的稳定性、光催化效率高及环境友好等优点， 自上世纪初就被广泛应用于颜料、 涂料、 化妆品、 环境保护、 新型能源等领域， 尤其是其优异的光催化性能， 使得人们对 Τ )2的研究越来越重视。 0 2 Semiconductor materials have been widely used in pigments, coatings, cosmetics, environmental protection, new energy sources, etc. since the beginning of the last century due to their good stability, high photocatalytic efficiency and environmental friendliness, especially their excellent light. The catalytic performance has made people pay more and more attention to the research of Τ) 2 .
以往研究发现， 1 02的光催化活性主要与其晶型、 形貌、 大小、 比表面积 及外露晶面等因素有关。 Τι02常见的晶型有三种： 板钛矿、 锐钛矿和金红石， 其中， 锐钛矿光催化活性最好， 金红石几乎不具备光催化活性， 板钛矿由于性 质不稳定， 一般研究较少。 近年相关研究发现， 在纯锐钛矿中加入适量的金红 石相 （锐钛矿 /金红石型混晶） 可显著提高二氧化钛的光催化活性。 这种现象可 解释为： 形成的异质结结构使得体系中能够俘获电子和空穴的陷阱增多， 可有 效分离光生电子-空穴对， 从而提高光催化活性， 上述现象也称为混晶效应。 形 貌方面， 三维分级结构的1 02微纳米材料具有微米、纳米结构性质优势的同时， 也抑制了二者结构上的缺陷， 表现出了优异的光催化性质。 分级 02微纳米材 料具有纳米级的基元结构， 缩短光生电子和空穴的迁移时间， 有效提高分离率， 从而提高了材料的光催化活性； 纳米级基元结构带来的另外一个性质优势是高 的比表面积。 高比表面积增大了光催化反应的接触面积， 从而提高了材料的光 催化活性； 微米级结构使得 1 02在使用过程中能够保持结构稳定性， 这是催化 剂走向使用化所必须具有的性能。 Previous studies found that the photocatalytic activity of 102 mainly its crystalline form, morphology, size, specific surface area and the exposed crystal plane factors and so on. There are three common crystal forms of Τι0 2 : brookite, anatase and rutile, among which anatase has the best photocatalytic activity, rutile has almost no photocatalytic activity, and brookite is less stable due to its unstable nature. . Recent studies have found that the addition of an appropriate amount of rutile phase (anatase/rutile mixed crystal) to pure anatase can significantly increase the photocatalytic activity of titanium dioxide. This phenomenon can be explained as follows: The formed heterojunction structure increases the number of traps capable of trapping electrons and holes in the system, and can effectively separate photogenerated electron-hole pairs, thereby improving photocatalytic activity. The above phenomenon is also called mixed crystal effect. . Morphology aspect, 102 micro-nano material having micron-dimensional hierarchical structure, the nature of the nanostructures advantages, also inhibited both structural defects, exhibited an excellent photocatalytic properties. The graded 02 micro-nano material has a nano-scale structure, shortens the migration time of photogenerated electrons and holes, and effectively increases the separation rate, thereby improving the photocatalytic activity of the material; another property advantage brought by the nano-scale structure is High specific surface area. High specific surface area increases the contact area of the photocatalytic reaction, thus improving the photocatalytic activity of a material; micron-scale structures 102 such that during use to maintain structural stability, which is the catalytic The performance that the agent must have to use.
已有研究通常只考虑单方面因素对 02光催化性能的影响， 将两种性质优 势相结合的研究还很少。 本发明使用溶胶-凝胶法与水热法联用的方法， 制备出 形貌新颖、 性能优异的分级混晶 02微纳米材料。 Existing studies usually only consider the influence of unilateral factors on the photocatalytic performance of 02 , and there are few studies combining the two advantages. The invention uses a sol-gel method and a hydrothermal method to prepare a graded mixed crystal 0 2 micro-nano material with novel morphology and excellent performance.
发明内容 Summary of the invention
本发明的目的之一在于提供一种形貌新颖、 性能优异的分级混晶 02微纳 米材料， 所述分级混晶 1 02微纳米材料为分级花状结构， 混晶晶相， 具有优异 的光催化活性和结构稳定性。 One of the objects of the present invention is to provide a graded mixed crystal 02 micro/nano material with novel morphology and excellent performance, and the graded mixed crystal 10 2 micro-nano material is a graded flower-like structure, a mixed crystal phase, and has excellent properties. Photocatalytic activity and structural stability.
为了达到上述目的， 本发明采用了如下技术方案：  In order to achieve the above object, the present invention adopts the following technical solutions:
一种分级混晶 1 02微纳米材料， 所述微纳米材料为纳米线组装形成的花状 结构， 所述花状结构的直径为 2~4μπι， 纳米线直径为 10~30nm， 纳米线长度为 0.9~2μπι, 晶型组成为锐钛矿-金红石型混晶。 花状结构的上下表面都可以充分 利用， 提高了分级混晶 Τ )2微纳米材料作为催化剂的催化活性和结构稳定性。 锐钛矿-金红石型的混晶效应同样提高了分级混晶 02微纳米材料作为催化剂 的催化活性。 本发明将花状分级微纳米结构与锐钛矿 -金红石型混晶结合起来， 得到了催化活性和结构稳定性均十分优异的分级混晶 1 02微纳米材料。 A graded mixed crystal 1 0 2 micro-nano material, wherein the micro-nano material is a flower-like structure formed by assembling nanowires, the diameter of the flower-like structure is 2~4μπι, the diameter of the nanowire is 10-30 nm, and the length of the nanowire It is 0.9~2μπι, and the crystal form is anatase-rutile mixed crystal. The upper and lower surfaces of the flower-like structure can be fully utilized to improve the catalytic activity and structural stability of the 2 micro-nano material as a catalyst. The anatase-rutile mixed crystal effect also enhances the catalytic activity of the graded mixed crystal 02 micro-nanomaterial as a catalyst. The invention combines the flower-like hierarchical micro-nano structure with the anatase-rutile mixed crystal to obtain a graded mixed crystal 10 2 micro-nano material which is excellent in catalytic activity and structural stability.
所述花状结构的直径为 2.2~3.6μπι， 例如 2.4μπι、 2.1μπι、 2.5μπι、 2.7μπι、 2.9μπι、 3.1μπι、 3.4μπι、 3.3μπι、 3.6μπι、 3.9μπι， 优选 2.4 3.4μπι。  The flower-like structure has a diameter of 2.2 to 3.6 μm, such as 2.4 μm, 2.1 μm, 2.5 μm, 2.7 μm, 2.9 μm, 3.1 μm, 3.4 μm, 3.3 μm, 3.6 μm, 3.9 μm, preferably 2.4 3.4 μm.
所述纳米线直径为 12~28nm,例如 11匪、 13匪、 16匪、 18匪、 20匪、 22匪、 24nm、 26nm、 28nm、 29nm, 优选 14~27nm。  The nanowires have a diameter of 12 to 28 nm, such as 11 Å, 13 Å, 16 Å, 18 Å, 20 Å, 22 Å, 24 nm, 26 nm, 28 nm, 29 nm, preferably 14 to 27 nm.
所述纳米线长度为 1.1~1.9μπι， 例如 1.2μπι、 1.3μπι、 1.4μπι、 1.5μπι、 1.6μπι、 1.7μπι、 1.8μπι、 1.9μπι， 优选 1.15~1.85μπι。  The nanowires have a length of 1.1 to 1.9 μm, such as 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, preferably 1.15 to 1.85 μm.
锐钛矿 -金红石型混晶中， 金红石相的质量百分比为 50~60%， 例如 50.5%、 51%、 51.5%、 52%、 52.5%、 53%、 53.5%、 54%、 54.5%、 55%、 55.5%、 56%、 56.5%、 57%、 57.5%、 58%、 58.5%、 59%、 59.5%, 优选 52~58%， 进一歩优选 53~57%。 In the anatase-rutile mixed crystal, the mass percentage of the rutile phase is 50 to 60%, for example, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59% 59.5%, preferably 52~58%, and further preferably 53~57%.
本发明的目的之二在于提供一种如上所述的分级混晶 02微纳米材料的制 备方法， 通过溶胶-凝胶法与水热法联用， 制备出纳米线为基元结构组成的花状 分级混晶 Ti02微纳米材料。 所述花状结构直径为 2~4μπι， 一维纳米线直径为 10~30nm， 纳米线长度为 0.9~2μπι， 晶型为锐钛矿-金红石型混晶。 A second object of the present invention is to provide a method for preparing a graded mixed crystal 02 micro-nano material as described above, which is prepared by a sol-gel method and a hydrothermal method to prepare a flower-like structure having a nanowire as a basic structure. Graded mixed crystal Ti0 2 micro-nano materials. The flower-like structure has a diameter of 2 to 4 μπι, a one-dimensional nanowire having a diameter of 10 to 30 nm, a nanowire length of 0.9 to 2 μπι, and a crystal form of an anatase-rutile mixed crystal.
一种如上所述的分级混晶 Τι02微纳米材料的制备方法， 所述方法包括如下 歩骤： A method for preparing a graded mixed crystal Τι 2 micro-nano material as described above, the method comprising the following steps:
( 1 ) 将钛的有机化合物滴加到醇水溶液中， 混合均匀， 静置， 得到溶胶； (1) adding an organic compound of titanium to an aqueous alcohol solution, mixing uniformly, and standing to obtain a sol;
(2) 将歩骤 （1 ) 得到的溶胶与盐酸冷凝回流， 得到白色乳状液； (2) condensing the sol obtained in the step (1) with hydrochloric acid to obtain a white emulsion;
( 3 ) 将歩骤 （2 ) 得到的白色乳状液离心， 洗涤， 干燥， 煅烧， 得到白色 粉末；  (3) centrifuging, washing, drying, and calcining the white emulsion obtained in the step (2) to obtain a white powder;
(4) 将歩骤 （3 ) 得到的白色粉末分散在 NaOH水溶液中， 反应；  (4) dispersing the white powder obtained in the step (3) in an aqueous solution of NaOH, and reacting;
( 5 ) 将歩骤 （4 ) 反应结束后得到的白色沉淀分离， 洗涤， 干燥， 得到分 级混晶 Ti02微纳米材料。 (5) The white precipitate obtained after the completion of the reaction of (5) is separated, washed, and dried to obtain a graded mixed crystal Ti0 2 micro/nano material.
所述钛的有机化合物选自钛酸四丁酯、 钛酸四异丙酯或钛酸四乙酯中的任 意一种或至少两种的混合物， 所述混合物例如钛酸四丁酯和钛酸四异丙酯的混 合物， 钛酸四乙酯和钛酸四丁酯的混合物， 钛酸四异丙酯和钛酸四乙酯的混合 物， 钛酸四丁酯、 钛酸四异丙酯和钛酸四乙酯的混合物， 优选钛酸四丁酯和 /或 钛酸四异丙酯， 进一歩优选钛酸四丁酯。  The organic compound of titanium is selected from any one or a mixture of at least two of tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate, such as tetrabutyl titanate and titanic acid. a mixture of tetraisopropyl ester, a mixture of tetraethyl titanate and tetrabutyl titanate, a mixture of tetraisopropyl titanate and tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate and titanium A mixture of tetraethyl acid, preferably tetrabutyl titanate and/or tetraisopropyl titanate, further preferably tetrabutyl titanate.
所述钛的有机化合物在醇水溶液中的浓度为 0.01~0.1mol/L， 例如 0.02mol/L、 0.03mol/L、 0.04mol/L、 0.05mol/L、 0.06mol/L、 0.07mol/L、 0.08mol/L、 0.09mol/L， 优选 0.015~0.095mol/L， 进一歩优选 0.025~0.085mol/L。 The concentration of the titanium organic compound in the aqueous alcohol solution is 0.01 to 0.1 mol/L, for example, 0.02 mol/L, 0.03 mol/L, 0.04 mol/L, 0.05 mol/L, 0.06 mol/L, and 0.07 mol/L. , 0.08mol/L, 0.09 mol/L, preferably 0.015 to 0.095 mol/L, and further preferably 0.025 to 0.085 mol/L.
优选地， 所述醇选自乙醇、 丙醇或丁醇中的任意一种或者至少两种的混合 物， 优选乙醇。  Preferably, the alcohol is selected from any one of ethanol, propanol or butanol or a mixture of at least two, preferably ethanol.
优选地， 所述醇水溶液为乙醇和水的溶液， 所述乙醇和水的体积比为 15:1-1 :15, 例如 14:1、 10:1、 1 :1、 1 :5、 1:10、 1 :14， 优选 10:1 1 :10， 进一歩优 选 5:1~1 :5。  Preferably, the aqueous alcohol solution is a solution of ethanol and water, and the volume ratio of the ethanol to water is 15:1 to 1:15, for example, 14:1, 10:1, 1:1, 1:5, 1: 10, 1 : 14, preferably 10:1 1 : 10, further preferably 5:1 to 1:5.
所述静置的时间为 10~15h， 例如 10.2h、 10.5h、 10.9h、 11.3h、 11.6h、 12.2h、 12.8h、 13.4h、 13.9h、 14.3h、 14.8h， 优选 10.5~14.5h， 进一歩优选 ll~14h。  The standing time is 10-15 h, for example 10.2 h, 10.5 h, 10.9 h, 11.3 h, 11.6 h, 12.2 h, 12.8 h, 13.4 h, 13.9 h, 14.3 h, 14.8 h, preferably 10.5 to 14.5 h. , a further preferred ll~14h.
所述冷凝回流在油浴中进行， 所述油浴的温度为 100 200 °C， 例如 110°C、 120°C、 130°C、 140°C、 150°C、 160°C、 170°C、 180°C、 190°C， 优选 105~195°C， 进一歩优选 115~185°C。  The condensing reflux is carried out in an oil bath having a temperature of 100 200 ° C, for example 110 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C 180 ° C, 190 ° C, preferably 105 ~ 195 ° C, further preferably 115 ~ 185 ° C.
所述冷凝回流的时间为 20~40h， 例如 21h、 24h、 26h、 28h、 30h、 32h、 34h、 36h、 38h， 优选 22~39h， 进一歩优选 25~35h。  The condensing reflux time is 20~40h, for example 21h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, preferably 22~39h, and further preferably 25~35h.
将歩骤（1 )得到的溶胶与盐酸冷凝回流， 盐酸的加入使得锐钛矿-金红石型 混晶的形成。  The sol obtained in the step (1) is condensed and refluxed with hydrochloric acid, and the addition of hydrochloric acid causes formation of an anatase-rutile mixed crystal.
所述盐酸与钛离子的摩尔比为 5:1~15:1， 例如 6:1、 7:1、 8:1、 9:1、 10:1、 11:1、 12:1、 13:1、 14:1， 优选 5.5:1~14.5:1， 进一歩优选 6.5:1 13.5:1。  The molar ratio of the hydrochloric acid to the titanium ion is 5:1 to 15:1, for example, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1 14:1, preferably 5.5:1~14.5:1, further preferably 6.5:1 13.5:1.
歩骤 （3 ) 用乙醇和去离子水洗涤沉淀物。  Step (3) Wash the precipitate with ethanol and deionized water.
歩骤 (3 )所述煅烧温度为 200 400 °C， 例如 210°C、 230°C、 250。C、 270。C、 290°C、 310°C、 330°C、 350°C、 370°C、 390 °C , 优选 220 380 °C， 进一歩优选 240~260。  The calcination temperature in the step (3) is 200 400 ° C, for example, 210 ° C, 230 ° C, 250. C, 270. C, 290 ° C, 310 ° C, 330 ° C, 350 ° C, 370 ° C, 390 ° C, preferably 220 380 ° C, further preferably 240 ~ 260.
优选地， 所述 NaOH水溶液的浓度为 5~10mol/L， 例如 5.5mol/L、 6mol/L、 6.5mol/L、 7mol/L、 7.5mol/L、 8mol/L、 8.5mol/L、 9mol/L、 9.5mol/L， 优选 5.8~9.8mol/L, 进一歩优选 6.3~9.2mol/L。 将白色粉末与 NaOH水溶液反应， 得 到分级结构的 1 02微纳米材料。 Preferably, the concentration of the aqueous NaOH solution is 5 to 10 mol/L, for example, 5.5 mol/L, 6 mol/L, 6.5 mol/L, 7 mol/L, 7.5 mol/L, 8 mol/L, 8.5 mol/L, and 9 mol. /L, 9.5mol/L, preferred 5.8~9.8mol/L, further 6.3~9.2mol/L. The white powder was reacted with an aqueous NaOH solution to obtain a hierarchical structure of a 10 2 micronanometer material.
所述 NaOH水溶液的体积为 30~70mL， 例如 34mL、 38mL、 42mL、 46mL、 51mL、 55mL、 59mL、 63mL、 67mL， 优选 35~65mL， 进一歩优选 40~60mL。  The volume of the aqueous NaOH solution is 30 to 70 mL, for example, 34 mL, 38 mL, 42 mL, 46 mL, 51 mL, 55 mL, 59 mL, 63 mL, 67 mL, preferably 35 to 65 mL, and further preferably 40 to 60 mL.
歩骤（4 )所述反应的温度为 120~200。C，例如 130。C、 140。C、 150。C、 160。C、 170°C、 180°C、 190°C， 优选 125~195°C， 进一歩优选 135~185°C。  The temperature of the reaction described in the step (4) is from 120 to 200. C, for example 130. C, 140. C, 150. C, 160. C, 170 ° C, 180 ° C, 190 ° C, preferably 125 to 195 ° C, further preferably 135 to 185 ° C.
歩骤（4 )所述反应的时间为 3~5h， 例如 3.2h、 3.4h、 3.6h、 3.8h、 4.1h、 4.3h、 4.6h、 4.8h， 优选 3.1~4.9h， 进一歩优选 3.3~4.7h。  The reaction time of the step (4) is 3~5h, for example 3.2h, 3.4h, 3.6h, 3.8h, 4.1h, 4.3h, 4.6h, 4.8h, preferably 3.1~4.9h, further preferably 3.3 ~4.7h.
歩骤 ( 5 ) 洗涤至 pH值为 6.5~7.5， 例如 6.55、 6.65、 6.75、 6.8、 6.9、 7、 7.1、 7.2， 优选 6.6~7.4， 进一歩优选 6.7~7.3。  Step (5) Wash to a pH of 6.5 to 7.5, such as 6.55, 6.65, 6.75, 6.8, 6.9, 7, 7.1, 7.2, preferably 6.6 to 7.4, and further preferably 6.7 to 7.3.
歩骤 （5 ) 所述分离选自过滤、 离心分离、 沉淀、 重力沉降或离心沉降中的 任意一种， 优选过滤或离心分离， 进一歩优选离心分离。  Step (5) The separation is selected from any one selected from the group consisting of filtration, centrifugation, precipitation, gravity sedimentation or centrifugal sedimentation, preferably filtration or centrifugation, followed by centrifugation.
一种如上所述的分级混晶 Ti02微纳米材料的制备方法， 所述方法包括如下 歩骤： A method for preparing a graded mixed crystal Ti 2 2 micro-nano material as described above, the method comprising the following steps:
( Γ ) 将钛酸四丁酯滴加到 100~200mL乙醇水溶液中， 钛酸四丁酯在乙醇 水溶液中的浓度为 0.01~0.1mol/L，乙醇与水的体积比为 1 :15~15: 1，混合均匀后， 静置 10~15h后得到溶胶；  ( Γ ) tetrabutyl titanate is added dropwise to 100~200mL ethanol solution, the concentration of tetrabutyl titanate in ethanol aqueous solution is 0.01~0.1mol/L, and the volume ratio of ethanol to water is 1:15~15 : 1, after mixing evenly, after standing for 10~15h, the sol is obtained;
( 2' ) 将歩骤 （Γ ) 得到的溶胶与盐酸在 100 200 °C的油浴中冷凝回流 20~40h， 得到白色乳状液；  ( 2 ' ) The sol obtained by the step (Γ) is condensed and refluxed with hydrochloric acid in an oil bath at 100 200 ° C for 20 to 40 hours to obtain a white emulsion;
(3' )将歩骤 (2，) 得到的白色乳状液离心， 洗涤， 干燥， 煅烧， 得到白色 粉末；  (3') centrifuging, washing, drying, and calcining the white emulsion obtained in the step (2,) to obtain a white powder;
(4' ) 将歩骤 （3' ) 得到的白色粉末分散在 30~70mL NaOH水溶液中， 置 于反应釜中反应； (5' ) 反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 6.5~7.5， 然后干燥即得分级混晶 1 02微纳米材料。 (4') dispersing the white powder obtained in the step (3') in a 30-70 mL NaOH aqueous solution, and placing the reaction in a reaction vessel; (5') After the reaction is completed, the obtained white precipitate is centrifuged, washed to a pH of 6.5 to 7.5, and then dried to obtain a graded mixed crystal of 10 2 micrometers.
一种如上所述的分级混晶 Ti02微纳米材料的用途，所述分级混晶 Τι02微纳 米材料用于光催化领域。 Classification purposes as described above mixed crystal micro-nano material Ti0 2, the hierarchical Τι0 2 mixed crystal material for a micro-nano photocatalysis.
与现有技术相比， 本发明具有如下有益效果：  Compared with the prior art, the present invention has the following beneficial effects:
( 1 )本发明所述分级混晶 1 02微纳米材料结合了花状分级纳米结构以及混 晶的优势， 具备优异的催化活性和结构稳定性； (1) The graded mixed crystal 1 0 2 micro-nano material of the present invention combines the advantages of flower-like hierarchical nanostructures and mixed crystals, and has excellent catalytic activity and structural stability;
(2)采用本发明的方法得到的分级混晶 Τ )2微纳米材料分散性好、产品纯 度高， 且制备方法环境友好， 反应条件温和， 能耗低， 材料具有高的光催化活 性和稳定性， 易于推广使用； (2) The graded mixed crystal obtained by the method of the invention) 2 micro-nano material has good dispersibility, high product purity, and the preparation method is environmentally friendly, the reaction condition is mild, the energy consumption is low, and the material has high photocatalytic activity and stability. Sexual, easy to promote;
( 3 )本发明分级混晶 Τι02微纳米材料在降解亚甲基蓝染料时的吸附性能和 光催化活性较 Degussa P25更优。 (3) The adsorption performance and photocatalytic activity of the graded mixed crystal Τι0 2 micro/nano material of the present invention in degrading methylene blue dye are superior to those of Degussa P25.
附图说明 DRAWINGS
下面结合附图并通过具体实施方式来进一歩说明本发明的技术方案。  The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.
图 1为实施例 1所制得的 Ti02材料的高倍 SEM图； 1 is a high-magnification SEM image of the Ti0 2 material prepared in Example 1;
图 2为实施例 1所制得的 Τι02材料的 SEM图； 2 is an SEM image of the Τι0 2 material obtained in Example 1;
图 3为实施例 1所制得的 Τι02材料的 XRD图； 3 is an XRD pattern of the Τι0 2 material prepared in Example 1;
图 4为实施例 1所制得的 Τ )2材料和商用 Ρ25降解亚甲基蓝溶液的光催化 效果对比图； 4 is a comparison diagram of photocatalytic effects of the ruthenium 2 material prepared in Example 1 and the commercial yttrium 25 degraded methylene blue solution;
图 5为实施例 2所制得的 Τι02材料的 SEM图； Figure 5 is an SEM image of the Τι0 2 material obtained in Example 2 ;
图 6为实施例 2所制得的 Τι02材料的 XRD图。 Fig. 6 is an XRD chart of the Τι0 2 material obtained in Example 2 .
具体实施方式 detailed description
为更好地说明本发明， 便于理解本发明的技术方案， 本发明的典型但非限 制性的实施例如下： In order to better explain the present invention, it is convenient to understand the technical solution of the present invention, and the typical but not limited of the present invention. The implementation of the system is as follows:
实施例 1  Example 1
( 1 )将 0.04mol/L的钛酸四丁酯滴加到 50mL乙醇和 80mL水混合溶液中， 混合均匀， 静置 10h后得到溶胶；  (1) 0.04 mol/L of tetrabutyl titanate was added dropwise to a mixed solution of 50 mL of ethanol and 80 mL of water, and the mixture was uniformly mixed, and after standing for 10 hours, a sol was obtained;
(2) 将歩骤 （1 ) 的溶胶与 0.4mol/L盐酸在 100°C的油浴下冷凝回流 22h， 得到白色乳状液；  (2) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 100 ° C for 22 hours to obtain a white emulsion;
(3 ) 将歩骤 （2) 中的白色乳状液离心分离， 洗涤并在烘箱中干燥， 马弗 炉中 300°C煅烧；  (3) centrifuging the white emulsion in the step (2), washing and drying in an oven, and calcining at 300 ° C in a muffle furnace;
(4)将歩骤 （3 ) 中的白色粉末分散在 7mol/L的 NaOH水溶液中， 置于反 应釜中 150°C水热反应 5h;  (4) Dispersing the white powder in the step (3) in a 7 mol/L NaOH aqueous solution, and placing it in a reaction vessel at 150 ° C for hydrothermal reaction for 5 hours;
(5) 反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 7， 然后 干燥即得分级混晶 02微纳米材料。  (5) After the reaction is completed, the obtained white precipitate is centrifuged, washed to a pH of 7, and then dried to obtain a graded mixed crystal 02 micro-nano material.
图 1、 图 2所示为实施例 1所制得的分级混晶 Ti02微纳米材料在不同倍率 下的 SEM图， 从图可以看出， 该花状微球的直径约为 3μπι， 由纳米线基元结构 组成， 纳米线直径约为 20nm， 长度约为 1μπι。 图 3为本实施例制得的分级混晶 Ή02微纳米材料的 XRD图谱， 表明所制得的三维花状 Τ )2材料同时具有锐钛 矿、金红石的晶型结构，即锐钛矿-金红石型混晶，其中，金红石相含量为 51.4%。 图 4为本实施例制得的分级混晶 Τι02微纳米材料与相同质量的 Degussa P25纳 米 Ti02加入相同浓度相同体积的亚甲基蓝溶液中，在黑暗条件下搅拌 lh以达到 吸脱附平衡后， 在紫外光照射下， 亚甲基蓝溶液浓度随时间的变化图， 显示出 较 Degussa P25更高的光催化性能。 Figure 1 and Figure 2 show the SEM images of the graded mixed crystal Ti0 2 micro/nano materials prepared in Example 1 at different magnifications. It can be seen from the figure that the diameter of the flower-like microspheres is about 3 μm, from nanometers. The line element is composed of a structure having a diameter of about 20 nm and a length of about 1 μm. 3 is an XRD pattern of the graded mixed crystal Ή0 2 micro-nano material prepared in the present embodiment, which indicates that the obtained three-dimensional flower-like Τ 2 material has both a crystal structure of anatase and rutile, namely anatase- A rutile type mixed crystal in which the rutile phase content is 51.4%. 4 is a mixed mixed crystal Τι 2 2 micro-nano material prepared in the present embodiment and the same mass of Degussa P25 nano-Ti0 2 is added to the same concentration of the same volume of methylene blue solution, and stirred under dark conditions for 1 hour to reach the adsorption-desorption equilibrium. The change in the concentration of methylene blue solution over time under UV light showed a higher photocatalytic performance than Degussa P25.
实施例 2  Example 2
( 1 )将 0.04mol/L的钛酸四丁酯滴加到 50mL乙醇和 80mL水混合溶液中， 混合均匀， 静置 10h后得到溶胶； (1) 0.04 mol/L of tetrabutyl titanate was added dropwise to a mixed solution of 50 mL of ethanol and 80 mL of water. Mix well, let stand for 10h to obtain sol;
(2) 将歩骤 （1) 的溶胶与 0.5mol/L盐酸在 100°C的油浴下冷凝回流 22h， 得到白色乳状液；  (2) The sol of step (1) is condensed and refluxed with 0.5 mol/L hydrochloric acid in an oil bath at 100 ° C for 22 hours to obtain a white emulsion;
(3) 将歩骤 （2) 中的白色乳状液离心分离， 洗涤并在烘箱中干燥， 马弗 炉中 300°C煅烧；  (3) Centrifuging the white emulsion in the step (2), washing and drying in an oven, and calcining at 300 ° C in a muffle furnace;
(4)将歩骤 （3) 中的白色粉末分散在 7mol/L的 NaOH水溶液中， 置于反 应釜中 150°C水热反应 5h;  (4) Dispersing the white powder in the step (3) in a 7 mol/L NaOH aqueous solution, and placing it in a reaction vessel at 150 ° C for hydrothermal reaction for 5 hours;
(5) 反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 7， 然后 干燥即得分级混晶 02微纳米材料。  (5) After the reaction is completed, the obtained white precipitate is centrifuged, washed to a pH of 7, and then dried to obtain a graded mixed crystal 02 micro-nano material.
图 5所示为实施例 2所制得的分级混晶 Ti02微纳米材料的 SEM图，从图可 以看出， 该花状微球的直径约为 2.5μπι， 由纳米线基元结构组成， 纳米线直径约 为 25nm，长度约为 900nm。图 6为本实施例制得的分级混晶 Ti02微纳米材料的 XRD图谱， 表明所制得的三维花状1102材料同时具有锐钛矿、 金红石的晶型结 构， 即锐钛矿-金红石型混晶， 其中， 金红石相含量为 57.3%。 FIG. 5 is a SEM image of the graded mixed crystal TiO 2 micro/nano material prepared in Example 2. As can be seen from the figure, the flower microsphere has a diameter of about 2.5 μm, and is composed of a nanowire primitive structure. The nanowires have a diameter of about 25 nm and a length of about 900 nm. 6 is an XRD pattern of the graded mixed crystal Ti0 2 micro/nano material prepared in the present embodiment, which indicates that the obtained three-dimensional flower-like 110 2 material has a crystal structure of anatase and rutile, that is, anatase-rutile. The mixed crystal, wherein the rutile phase content is 57.3%.
实施例 3  Example 3
(1)将 0.04mol/L的钛酸四丁酯滴加到 50mL乙醇和 50mL水混合溶液中， 混合均匀， 静置 12h后得到溶胶；  (1) 0.04 mol/L of tetrabutyl titanate was added dropwise to a mixed solution of 50 mL of ethanol and 50 mL of water, mixed uniformly, and allowed to stand for 12 hours to obtain a sol;
(2) 将歩骤 （1) 的溶胶与 0.4mol/L盐酸在 100°C的油浴下冷凝回流 24h， 得到白色乳状液；  (2) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 100 ° C for 24 hours to obtain a white emulsion;
(3) 将歩骤 （2) 中的白色乳状液离心分离， 洗涤并在烘箱中干燥， 马弗 炉中 300°C煅烧；  (3) Centrifuging the white emulsion in the step (2), washing and drying in an oven, and calcining at 300 ° C in a muffle furnace;
(4)将歩骤 （3) 中的白色粉末分散在 7mol/L的 NaOH水溶液中， 置于反 应釜中 150°C水热反应 5h; (5) 反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 7， 然后 干燥即得分级混晶 02微纳米材料。 (4) Dispersing the white powder in the step (3) in a 7 mol / L aqueous solution of NaOH, placed in a reaction vessel at 150 ° C hydrothermal reaction for 5 h; (5) After the reaction is completed, the obtained white precipitate is centrifuged, washed to a pH of 7, and then dried to obtain a graded mixed crystal 02 micronanometer material.
SEM图显示， 该花状微球的直径约为 3μπι， 由纳米线基元结构组成， 纳米 线直径约为 15nm， 长度约为 1.2μπι。 XRD图谱显示所制得的三维花状 Τι02材 料同时具有锐钛矿、 金红石的晶型结构， 即锐钛矿-金红石型混晶， 其中， 金红 石相含量为 54.3%。 The SEM image shows that the flower-like microspheres have a diameter of about 3 μm, and are composed of nanowire motifs. The nanowires have a diameter of about 15 nm and a length of about 1.2 μm. The XRD pattern shows that the three-dimensional flower-like Τι0 2 material has a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 54.3%.
实施例 4  Example 4
( 1 )将 0.04mol/L的钛酸四丁酯滴加到 50mL乙醇和 80mL水混合溶液中， 混合均匀， 静置 15h后得到溶胶；  (1) 0.04 mol/L of tetrabutyl titanate was added dropwise to a mixed solution of 50 mL of ethanol and 80 mL of water, and the mixture was uniformly mixed, and allowed to stand for 15 hours to obtain a sol;
(2) 将歩骤 （1 ) 的溶胶与 0.4mol/L盐酸在 110°C的油浴下冷凝回流 24h， 得到白色乳状液；  (2) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 110 ° C for 24 hours to obtain a white emulsion;
(3 ) 将歩骤 （2) 中的白色乳状液离心分离， 洗涤并在烘箱中干燥， 马弗 炉中 400°C煅烧；  (3) centrifuging the white emulsion in the step (2), washing and drying in an oven, and calcining at 400 ° C in a muffle furnace;
(4)将歩骤 （3 ) 中的白色粉末分散在 8mol/L的 NaOH水溶液中， 置于反 应釜中 150°C水热反应 5h;  (4) Dispersing the white powder in the step (3) in an 8 mol/L NaOH aqueous solution, and placing it in a reaction vessel at 150 ° C for 5 h;
(5) 反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 7， 然后 干燥即得分级混晶 02微纳米材料。  (5) After the reaction is completed, the obtained white precipitate is centrifuged, washed to a pH of 7, and then dried to obtain a graded mixed crystal 02 micro-nano material.
SEM图显示， 该花状微球的直径约为 3.5μπι， 由纳米线基元结构组成， 纳 米线直径约为 30nm， 长度约为 1.5μπι。 XRD图谱显示所制得的三维花状 Ti02 材料同时具有锐钛矿、 金红石的晶型结构， 即锐钛矿-金红石型混晶， 其中， 金 红石相含量为 52%。 The SEM image shows that the flower-like microspheres have a diameter of about 3.5 μm and are composed of a nanowire matrix structure having a nanowire diameter of about 30 nm and a length of about 1.5 μm. The XRD pattern shows that the three-dimensional flower-like Ti0 2 material has both a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 52%.
实施例 5  Example 5
( 1 )将 0.05mol/L的钛酸四丁酯滴加到 50mL乙醇和 80mL水混合溶液中， 混合均匀， 静置 10h后得到溶胶； (1) 0.05 mol/L of tetrabutyl titanate was added dropwise to a mixed solution of 50 mL of ethanol and 80 mL of water. Mix well, let stand for 10h to obtain sol;
(2) 将歩骤 （1 ) 的溶胶与 0.4mol/L盐酸在 100°C的油浴下冷凝回流 24h， 得到白色乳状液；  (2) The sol of step (1) is condensed and refluxed with 0.4 mol/L hydrochloric acid in an oil bath at 100 ° C for 24 hours to obtain a white emulsion;
(3 ) 将歩骤 （2) 中的白色乳状液离心分离， 洗涤并在烘箱中干燥， 马弗 炉中 400°C煅烧；  (3) centrifuging the white emulsion in the step (2), washing and drying in an oven, and calcining at 400 ° C in a muffle furnace;
(4)将歩骤 （3 ) 中的白色粉末分散在 8mol/L的 NaOH水溶液中， 置于反 应釜中 180°C水热反应 3h;  (4) Dispersing the white powder in the step (3) in an 8 mol/L NaOH aqueous solution, and placing it in a reaction kettle at 180 ° C for hydrothermal reaction for 3 hours;
(5)反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 7.5， 然后 干燥即得分级混晶 02微纳米材料。  (5) After the completion of the reaction, the obtained white precipitate was centrifuged, washed to a pH of 7.5, and then dried to obtain a graded mixed crystal 02 micronanometer material.
SEM图显示， 该花状微球的直径约为 3μπι， 由纳米线基元结构组成， 纳米 线直径约为 25nm， 长度约为 1μπι。 XRD图谱显示所制得的三维花状 Τι02材料 同时具有锐钛矿、 金红石的晶型结构， 即锐钛矿-金红石型混晶， 其中， 金红石 相含量为 53.5%。 The SEM image shows that the flower-like microspheres have a diameter of about 3 μm and consist of a nanowire matrix structure having a diameter of about 25 nm and a length of about 1 μm. The XRD pattern shows that the three-dimensional flower-like Τι0 2 material has a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 53.5%.
实施例 6  Example 6
( 1 )将 0.01mol/L的钛酸四丁酯滴加到 150mL乙醇和 10mL水混合溶液中， 混合均匀， 静置 12h后得到溶胶；  (1) 0.01 mol/L of tetrabutyl titanate was added dropwise to a mixed solution of 150 mL of ethanol and 10 mL of water, and the mixture was uniformly mixed, and after standing for 12 hours, a sol was obtained;
(2)将歩骤（1 ) 的溶胶与 0.05mol/L盐酸在 200°C的油浴下冷凝回流 20h， 得到白色乳状液；  (2) The sol of the step (1) is condensed and refluxed with 0.05 mol/L hydrochloric acid in an oil bath at 200 ° C for 20 hours to obtain a white emulsion;
(3 ) 将歩骤 （2) 中的白色乳状液离心分离， 洗涤并在烘箱中干燥， 马弗 炉中 200°C煅烧；  (3) centrifuging the white emulsion in the step (2), washing and drying in an oven, and calcining at 200 ° C in a muffle furnace;
(4)将歩骤 （3 ) 中的白色粉末分散在 5mol/L的 NaOH水溶液中， 置于反 应釜中 120°C水热反应 5h;  (4) Dispersing the white powder in the step (3) in a 5 mol/L NaOH aqueous solution, and placing it in a reaction kettle at 120 ° C for hydrothermal reaction for 5 hours;
(5)反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 6.5， 然后 干燥即得分级混晶 02微纳米材料。 (5) After the reaction is completed, the obtained white precipitate is centrifuged, washed to a pH of 6.5, and then Dry, ie, graded mixed crystal 02 micro-nano material.
SEM图显示， 该花状微球的直径约为 2μπι， 由纳米线基元结构组成， 纳米 线直径约为 10nm， 长度约为 1μπι。 XRD图谱显示所制得的三维花状 Τι02材料 同时具有锐钛矿、 金红石的晶型结构， 即锐钛矿-金红石型混晶， 其中， 金红石 相含量为 50.2%。 The SEM image shows that the flower-like microspheres have a diameter of about 2 μm and consist of a nanowire matrix structure having a diameter of about 10 nm and a length of about 1 μm. The XRD pattern shows that the three-dimensional flower-like Τι0 2 material has a crystal structure of anatase and rutile, that is, an anatase-rutile mixed crystal, wherein the rutile phase content is 50.2%.
实施例 7  Example 7
( 1 )将 O.lmol/L的钛酸四丁酯滴加到 10mL乙醇和 150mL水混合溶液中， 混合均匀， 静置 12h后得到溶胶；  (1) O.lmol/L tetrabutyl titanate was added dropwise to a mixed solution of 10 mL of ethanol and 150 mL of water, mixed uniformly, and allowed to stand for 12 hours to obtain a sol;
(2) 将歩骤 （1 ) 的溶胶与 1.5mol/L盐酸在 100°C的油浴下冷凝回流 40h， 得到白色乳状液；  (2) The sol of step (1) is condensed and refluxed with 1.5 mol/L hydrochloric acid in an oil bath at 100 ° C for 40 hours to obtain a white emulsion;
(3 ) 将歩骤 （2) 中的白色乳状液离心分离， 洗涤并在烘箱中干燥， 马弗 炉中 300°C煅烧；  (3) centrifuging the white emulsion in the step (2), washing and drying in an oven, and calcining at 300 ° C in a muffle furnace;
(4) 将歩骤 （3 ) 中的白色粉末分散在 10mol/L的 NaOH水溶液中， 置于 反应釜中 200 °C水热反应 3h;  (4) Dispersing the white powder in the step (3) in a 10 mol/L NaOH aqueous solution, and placing it in a reaction vessel at 200 ° C for 3 h;
(5) 反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 7， 然后 干燥即得分级混晶 02微纳米材料。  (5) After the reaction is completed, the obtained white precipitate is centrifuged, washed to a pH of 7, and then dried to obtain a graded mixed crystal 02 micro-nano material.
SEM图显示， 该花状微球的直径约为 4μπι， 由纳米线基元结构组成， 纳米 线直径约为 20nm， 长度约为 2μπι。 XRD图谱显示所制得的三维花状 Ti02材料 同时具有锐钛矿、 金红石的晶型结构， 即锐钛矿-金红石型混晶， 其中， 金红石 The SEM image shows that the flower-like microspheres have a diameter of about 4 μm, and are composed of a nanowire matrix structure. The nanowires have a diameter of about 20 nm and a length of about 2 μm. The XRD pattern shows that the three-dimensional flower-like Ti0 2 material has both the anatase and rutile crystal structure, that is, an anatase-rutile mixed crystal, among which, rutile
申请人声明， 本发明通过上述实施例来说明本发明的详细方法， 但本发明 并不局限于上述详细方法， 即不意味着本发明必须依赖上述详细方法才能实施。 所属技术领域的技术人员应该明了， 对本发明的任何改进， 对本发明产品各原 料的等效替换及辅助成分的添加、 具体方式的选择等， 均落在本发明的保护范 围和公开范围之内。 The Applicant declares that the present invention illustrates the detailed method of the present invention by the above embodiments, but the present invention It is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by relying on the above detailed methods. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, and addition of auxiliary components, selection of specific means, etc., are all within the scope of the present invention.

Claims

权 利 要 求 书 claims
1、一种分级混晶 1 02微纳米材料， 其特征在于， 所述微纳米材料为纳米线 组装形成的花状结构， 所述花状结构的直径为 2~4μπι， 纳米线直径为 10~30nm， 纳米线长度为 0.9~2μπι， 晶型组成为锐钛矿-金红石型混晶。 1. A graded mixed crystal 102 micro-nano material, characterized in that the micro-nano material is a flower-like structure formed by the assembly of nanowires, the diameter of the flower-like structure is 2~4 μm, and the diameter of the nanowire is 10 ~30nm, the length of the nanowire is 0.9~2μm, and the crystal composition is anatase-rutile mixed crystal.
2、如权利要求 1所述的 Ή02微纳米材料， 其特征在于， 所述花状结构的直 径为 2.2~3.6μπι， 优选 2.4~3.4μπι; 2. The Ή02 micro-nano material according to claim 1, characterized in that the diameter of the flower-like structure is 2.2~3.6 μm, preferably 2.4~3.4 μm;
优选地， 所述纳米线直径为 12~28nm， 优选 14~27nm; Preferably, the diameter of the nanowire is 12~28nm, preferably 14~27nm;
优选地， 所述纳米线长度为 1.1~1.9μπι， 优选 1.15~1.85μπι; Preferably, the length of the nanowire is 1.1~1.9 μm, preferably 1.15~1.85 μm ;
优选地， 锐钛矿 -金红石型混晶中， 金红石相的质量百分比为 50~60%， 优 选 52~58%， 进一歩优选 53~57%。 Preferably, in the anatase-rutile mixed crystal, the mass percentage of the rutile phase is 50~60%, preferably 52~58%, and further preferably 53~57%.
3、一种如权利要求 1或 2所述的分级混晶 Τι02微纳米材料的制备方法， 其 特征在于， 所述方法包括如下歩骤： 3. A method for preparing hierarchical mixed crystal TIO 2 micro-nano materials as claimed in claim 1 or 2, characterized in that the method includes the following steps:
( 1 ) 将钛的有机化合物滴加到醇水溶液中， 混合均匀， 静置， 得到溶胶； (1) Add titanium organic compounds dropwise into the alcohol aqueous solution, mix evenly, and let stand to obtain a sol;
(2) 将歩骤 （1 ) 得到的溶胶与盐酸冷凝回流， 得到白色乳状液； (2) Condensate and reflux the sol obtained in step (1) with hydrochloric acid to obtain a white emulsion;
( 3 ) 将歩骤 （2 ) 得到的白色乳状液离心， 洗涤， 干燥， 煅烧， 得到白色 粉末； (3) Centrifuge the white emulsion obtained in step (2), wash, dry and calcine to obtain white powder;
(4) 将歩骤 （3 ) 得到的白色粉末分散在 NaOH水溶液中， 反应； (4) Disperse the white powder obtained in step (3) in the NaOH aqueous solution and react;
( 5 ) 将歩骤 （4 ) 反应结束后得到的白色沉淀分离， 洗涤， 干燥， 得到分 级混晶 Ti02微纳米材料。 (5) Separate the white precipitate obtained after the reaction in step (4) is completed, wash and dry to obtain graded mixed crystal Ti0 2 micro-nano material.
4、 如权利要求 3所述的方法， 其特征在于， 所述钛的有机化合物选自钛酸 四丁酯、 钛酸四异丙酯或钛酸四乙酯中的任意一种或至少两种的混合物， 优选 钛酸四丁酯和 /或钛酸四异丙酯， 进一歩优选钛酸四丁酯； 4. The method of claim 3, wherein the titanium organic compound is selected from any one or at least two of tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate. A mixture of, preferably tetrabutyl titanate and/or tetraisopropyl titanate, and further preferably tetrabutyl titanate;
优选地， 所述钛的有机化合物在醇水溶液中的浓度为 0.01~0.1mol/L， 优选 0.015~0.095mol/L, 进一歩优选 0.025-0.085mol/L; 优选地， 所述醇选自乙醇、 丙醇或丁醇中的任意一种或者至少两种的混合 物， 优选乙醇； Preferably, the concentration of the titanium organic compound in the alcohol aqueous solution is 0.01~0.1mol/L, preferably 0.015~0.095mol/L, further preferably 0.025-0.085mol/L ; Preferably, the alcohol is selected from any one or a mixture of at least two of ethanol, propanol or butanol, preferably ethanol;
优选地， 所述醇水溶液为乙醇和水的溶液， 所述乙醇和水的体积比为 Preferably, the alcohol aqueous solution is a solution of ethanol and water, and the volume ratio of the ethanol and water is
15:1-1 :15, 优选 10:1 1 :10， 进一歩优选 5:1~1 :5。 15:1-1:15, preferably 10:1 1:10, and further preferably 5:1~1:5.
5、如权利要求 3或 4所述的方法，其特征在于，所述静置的时间为 10~15h， 优选 10.5~14.5h， 进一歩优选 ll~14h; 5. The method according to claim 3 or 4, characterized in that the standing time is 10~15h, preferably 10.5~14.5h, further preferably 11~14h;
优选地， 所述冷凝回流在油浴中进行， 所述油浴的温度为 100 200 °C， 优选 105~195。C， 进一歩优选 115 185 °C ; Preferably, the condensation reflux is performed in an oil bath, and the temperature of the oil bath is 100-200°C, preferably 105-195°C. C, further preferably 115-185 °C;
优选地，所述冷凝回流的时间为 20~40h，优选 22~39h，进一歩优选 25~35h。 Preferably, the condensation reflux time is 20~40h, preferably 22~39h, and further preferably 25~35h.
6、 如权利要求 3-5之一所述的方法， 其特征在于， 所述盐酸与钛离子的摩 尔比为 5:1~15:1， 优选 5.5:1~14.5:1， 进一歩优选 6.5:1 13.5:1； 6. The method according to any one of claims 3 to 5, characterized in that the molar ratio of hydrochloric acid to titanium ions is 5:1~15:1, preferably 5.5:1~14.5:1, further preferably 6.5 :1 13.5:1;
优选地， 歩骤 （3 ) 用乙醇和去离子水洗涤沉淀物； Preferably, step (3) washes the precipitate with ethanol and deionized water;
优选地， 歩骤 （3 ) 所述煅烧温度为 200~400°C， 优选 220~380°C， 进一歩 优选 240 260 °C。 Preferably, the calcination temperature in step (3) is 200~400°C, preferably 220~380°C, and further preferably 240-260°C.
7、 如权利要求 3-6之一所述的方法， 其特征在于， 所述 NaOH水溶液的浓 度为 5~10mol/L， 优选 5.8~9.8mol/L， 进一歩优选 6.3~9.2mol/L; 7. The method according to one of claims 3-6, characterized in that the concentration of the NaOH aqueous solution is 5~10mol/L, preferably 5.8~9.8mol/L, further preferably 6.3~9.2mol/L;
优选地， 所述 NaOH水溶液的体积为 30~70mL， 优选 35~65mL， 进一歩优 选 40~60mL; Preferably, the volume of the NaOH aqueous solution is 30 to 70 mL, preferably 35 to 65 mL, and further preferably 40 to 60 mL;
优选地， 歩骤 （4) 所述反应的温度为 120 200 °C， 优选 125~195°C， 进一 歩优选 135~185°C ; Preferably, the reaction temperature in step (4) is 120-200°C, preferably 125~195°C, and further preferably 135~185°C;
优选地， 歩骤 （4) 所述反应的时间为 3~5h， 优选 3.1~4.9h， 进一歩优选 Preferably, the reaction time in step (4) is 3~5h, preferably 3.1~4.9h, further preferably
8、 如权利要求 3-7之一所述的方法， 其特征在于， 歩骤 （5) 洗涤至 pH值 8. The method according to one of claims 3-7, characterized in that step (5) washes to pH value
6.5-7.5, 优选 6.6~7.4， 进一歩优选 6.7~7.3; 6.5-7.5, preferably 6.6~7.4, further preferably 6.7~7.3;
优选地， 歩骤 （5) 所述分离选自过滤、 离心分离、 沉淀、 重力沉降或离心 沉降中的任意一种， 优选过滤或离心分离， 进一歩优选离心分离。 Preferably, the separation in step (5) is selected from any one of filtration, centrifugal separation, sedimentation, gravity sedimentation or centrifugal sedimentation, preferably filtration or centrifugal separation, and further preferably centrifugal separation.
9、如权利要求 3-8之一所述的方法， 其特征在于， 所述方法包括如下歩骤： (Γ) 将钛酸四丁酯滴加到 100~200mL乙醇水溶液中， 钛酸四丁酯在乙醇 水溶液中的浓度为 0.01~0.1mol/L，乙醇与水的体积比为 1:15~15:1，混合均匀后， 静置 10~15h后得到溶胶； 9. The method according to any one of claims 3 to 8, characterized in that, the method includes the following steps: (1) Dropwise adding tetrabutyl titanate into 100~200 mL ethanol aqueous solution, tetrabutyl titanate The concentration of the ester in the ethanol aqueous solution is 0.01~0.1mol/L, and the volume ratio of ethanol to water is 1:15~15:1. After mixing evenly, let it stand for 10~15h to obtain the sol;
(2') 将歩骤 （Γ) 得到的溶胶与盐酸在 100 200 °C的油浴中冷凝回流 20~40h， 得到白色乳状液； (2') Condensate and reflux the sol obtained in step (1) and hydrochloric acid in an oil bath at 100-200 °C for 20~40h to obtain a white emulsion;
(3')将歩骤 (2，) 得到的白色乳状液离心， 洗涤， 干燥， 煅烧， 得到白色 粉末； (3') Centrifuge the white emulsion obtained in step (2,), wash, dry and calcine to obtain white powder;
(4') 将歩骤 （3') 得到的白色粉末分散在 30~70mL NaOH水溶液中， 置 于反应釜中反应； (4') Disperse the white powder obtained in step (3') in 30~70mL NaOH aqueous solution, and place it in a reaction kettle for reaction;
(5') 反应完毕后， 将得到的白色沉淀离心分离， 洗涤至 pH值为 6.5~7.5， 然后干燥即得分级混晶 102微纳米材料。 (5') After the reaction is completed, the obtained white precipitate is centrifuged, washed until the pH value is 6.5~7.5, and then dried to obtain hierarchical mixed crystals of 10 2 micro-nano materials.
10、 一种如权利要求 1或 2所述的分级混晶1102微纳米材料的用途， 其特 征在于， 所述分级混晶 02微纳米材料用于光催化领域。 10. The use of the graded mixed crystal 110 2 micro-nano material as claimed in claim 1 or 2, characterized in that the graded mixed crystal 0 2 micro-nano material is used in the field of photocatalysis.
PCT/CN2013/080138 2013-01-29 2013-07-25 Graded mixed crystal tio2 micro/nano material, preparation method therefor and application thereof WO2014117487A1 (en)

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