CN101070184A - Method for preparing single dispersing ball-shape mesoporous titanium dioxide colloid particles whose size and apparance are controllable - Google Patents
Method for preparing single dispersing ball-shape mesoporous titanium dioxide colloid particles whose size and apparance are controllable Download PDFInfo
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- CN101070184A CN101070184A CN 200610011885 CN200610011885A CN101070184A CN 101070184 A CN101070184 A CN 101070184A CN 200610011885 CN200610011885 CN 200610011885 CN 200610011885 A CN200610011885 A CN 200610011885A CN 101070184 A CN101070184 A CN 101070184A
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Abstract
The invention belongs to the field of preparing material of nanometer and sub-micron of inorganic semiconductor, it is especially relates to the preparation method of colloid granule of TiO2 whose size is between dozens of nanometers and dozens of sub-microns, whose pattern can be controlled, which is monodisperse and has spherical mesoporous. At room temperature, wrap up and cover a layer of TiO2 on surface of polymeric microballoon sphere (PSMMA) and then swell and infiltrate it through the mixed solution of toluene or tetrahydrofuran and ethanol, make colloid granule of TiO2 which is monodisperse and which has spherical mesoporous after getting even complex granule. The preparation method of this invention is simple, the colloid granule of TiO2 has high purity and good dispersibility, diameter of the granule is between 20-2000 nanometer, specific area is between 50-1000m2/g, the size of the granule distributes narrowly and the warp is smaller than 10%, and the size of granule can be controlled through the covering thickness of TiO2 and size of granule of PSMMA .
Description
Technical field
The invention belongs to inorganic semiconductor nanometer and submicron material preparation field, particularly tens nanometers are to the size of submicron and pattern preparation method controlled, monodispersed, spherical mesoporous titanium oxide colloid particle.
Background technology
Titanium dioxide is commonly called as titanium white, it is the more high function fine inorganic material of research, be important pottery, semi-conductor and catalytic material, because nanometer and mesoporous TiO 2 have very high specific surface area, special performances such as good weathering resistance, chemical resistance, higher chemical stability, thermostability, nontoxicity, photolytic activity, so be widely used in fields such as chemical industry, electronics, biology, coating, transmitter, dielectric materials, plastics, printing ink, papermaking, chemical fibre, rubber, separation, for example:
(1) TiO
2It is good photocatalyst, especially when they have meso-hole structure and nano-scale, because specific surface area increases, the key attitude on surface is different with granule interior, surface atom coordination deficiencies etc. form rough atomic steps, have strengthened the reaction contact surface, cause the activity site on surface to increase, reactive behavior increases greatly.
(2) mesoporous TiO
2Have big specific surface area and good thermostability, therefore can be as carrier, load various types of metallic nano particle, as nanometer gold, platinum etc., the cooperative photocatalysis activity of this matrix material improves greatly, and this respect research at present is a focus.
(3) in addition owing to have the spherical TiO of meso-hole structure
2Has the good adsorption performance, with this spherical TiO with meso-hole structure
2Colloidal solid is filmed, and the nanometer silver of load different size and metallic particles form colorful photochromic films then, in the jewel assembling, and photo chromic glass, aspects such as color photocopying paper, optics memory device have great application prospect.
(4) in addition, because TiO
2Have high refractive index, so monodisperse spherical TiO
2Colloidal solid comprises that the spheroidal particle with meso-hole structure is an optimal candidate material in photonic crystal and the colloidal crystal research.
Based on research and the requirement of using, especially satisfy at photoelectric device and assemble, as: the requirement of Electronic Paper, flat-panel monitor, photonic crystal and aspects such as colloidal crystal assembly device and uniform coating, spherical colloidal particle particle diameter with meso-hole structure should narrowly distributing, the pattern homogeneous, preparation process is simple as much as possible.Prepare monodisperse spherical mesoporous TiO on the document at present
2The method of colloidal solid mainly is with mesoporous carbon spheres and mesoporous SiO
2Ball is a template, with the titanic acid ester is raw material, it is penetrated into hydrolysis in the mesoporous carbon spheres template, removing template then makes, for example this method of employing such as Yi Tang has prepared the mesopore metal oxide ball (referring to document " General synthesis of mesoporous spheres of metal ofoxi des and phosphates ", J.Am.Chem.Soc., 4976～4977 pages of 2003 the 125th phases), this method shortcoming is that more complicated is time-consuming.Yunxia Zhang etc. directly prepares mesoporous TiO by introduce surfactivity in pure system in addition
2Colloidal solid is (referring to document " The formation ofmesoporous TiO
2Spheres via a facie chemical process ", J.Phys.Chem.B, volume was 5478～5481 pages in 2005 109), but above method gained particulate monodispersity is poor, and appearance and size is wayward.
Summary of the invention
Main purpose of the present invention is the shortcoming that overcomes above method, provides a kind of size and pattern controlled monodisperse spherical mesoporous TiO
2The preparation method of colloidal solid, the mesoporous TiO of gained
2The particle size range of colloidal solid is in 20～2000 nanometers, and the particle size distribution average deviation is less than 10%, and specific grain surface is long-pending between 50～1000m
2/ g.
It is template that the present invention adopts the multipolymer ball, by the swelling permeating method, has successfully prepared monodispersed spherical mesoporous TiO first
2Colloidal solid.
The objective of the invention is to realize by following technical scheme:
In the mixed solvent system at ambient temperature, form the coated by titanium dioxide layer on copolymer microsphere [vinylbenzene-Sipacril 2739OF microballoon (PSMMA)] surface, then the gained coatedparticles is used mixing solutions swelling osmotic treated, obtain polymkeric substance/titanium dioxide compound particle, more this composite particles sintering is obtained monodisperse spherical mesoporous titanium oxide colloid particle.
Preparation method of the present invention may further comprise the steps:
(1) dehydrated alcohol and the polar solvent volume ratio by 1: 15～15: 1 is mixed;
(2) with titanic acid ester [Ti (OR)
4] be dissolved in the mixed solvent of step (1) gained, stir, wherein the starting point concentration of titanic acid ester is 1 * 10
-4～5 mol; Be preferably 5 * 10
-4～1.5 mol;
(3) with water or ammonia solvent in the mixed solvent of step (1) gained, stir, and then add a certain amount of self-control or commercially available vinylbenzene-Sipacril 2739OF microballoon is uniformly dispersed, wherein the starting point concentration of ammonia is 0.01～5 mol, the starting point concentration of water is 0.01～5 mol, and the starting point concentration of vinylbenzene-Sipacril 2739OF microballoon is 0.01～100 grams per liter;
(4) at ambient temperature, the solution of step (3) preparation is joined in the reactor, titanic acid ester mixed solvent solution with step (2) preparation joins in the reactor then, wherein step (2) is 1: 5～5: 1 with the volume ratio of step (3) solution, stirring reaction 0.5～10 hour, obtain oyster white or white opacity liquid, centrifugation obtains the colloidal solid of vinylbenzene-Sipacril 2739OF microsphere surface cladding titanium dioxide;
(5) colloidal solid of the vinylbenzene that step (4) is obtained-Sipacril 2739OF microsphere surface cladding titanium dioxide is distributed in the mixing solutions of ethanol and organic solvent, wherein organic solvent and alcoholic acid volume ratio are 1: 9～9: 1, stirred 5～48 hours, centrifugation obtains the titanium dioxide/vinylbenzene-Sipacril 2739OF microballoon composite particles of homogeneous;
(6) homogeneous titanium dioxide/vinylbenzene that step (5) is obtained-Sipacril 2739OF microballoon composite particles is 350～1000 ℃ of following sintering 1～5 hour in temperature, obtain monodisperse spherical mesoporous titanium oxide colloid particle, the particle size distribution average deviation is less than 10%, the particulate diameter is in 20～2000 nanometers, and specific surface area is between 50～1000m
2/ g.
Described polar solvent is acetone, acetonitrile or Virahol etc.
Described titanic acid ester [Ti (OR)
4] in R be-C
nH
2n+1, n=2～4.
Described vinylbenzene-Sipacril 2739OF diameter of micro ball scope is that 30nm is to 5 μ m.
Described organic solvent is toluene or tetrahydrofuran (THF).
Effect of the present invention and advantage:
The mesoporous TiO that adopts method of the present invention to obtain
2Colloidal solid is the sphere of homogeneous, good dispersity, and narrow size distribution, particle size distribution average deviation be less than 10%, and have meso-hole structure, and specific surface area is at 50～1000m
2In/g the scope, as shown in Figure 1.
The present invention is by ethanol and the organic solution mixed solution TiO with the PSMMA surface
2Disperse to form nano level TiO
2Particle simultaneously with the PSMMA swelling, makes scattered nano-TiO
2Particle is easy to be penetrated into swollen PSMMA granule interior, forms the PSMMA/TiO of homogeneous
2Composite particles forms the mesoporous TiO 2 particle by calcining again.
Hydrolysis method of the present invention not only energy consumption is low, and the product purity height can also be controlled the mesoporous TiO 2 particle size by coated by titanium dioxide thickness and used PSMMA particulate size.
The present invention prepares single dispersion, spherical mesoporous TiO
2The method of colloidal solid is simple relatively, is easy to apply, and solvent for use is inexpensive, be easy to get, safety.
Further the present invention will be described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1. embodiments of the invention 1 monodisperse spherical mesoporous TiO
2The particle transmission electron microscope photo.
Embodiment
Embodiment 1
(1) dehydrated alcohol and the acetonitrile volume ratio by 1: 2 is mixed;
(2) tetrabutyl titanate is dissolved in the mixed solvent of step (1) gained, stirs, wherein the starting point concentration of tetrabutyl titanate is 2 * 10
-3Mol;
(3) ammoniacal liquor is added in the mixed solvent of step (1) gained, stirs, and then the PSMMA ball that to add a certain amount of commercially available diameter be 220nm is uniformly dispersed, wherein the starting point concentration of ammonia is 0.1 mol, and the starting point concentration of PSMMA ball is 0.02 grams per liter;
(4) at ambient temperature, the solution of step (3) preparation is joined in the reactor, tetrabutyl titanate mixed solvent solution with step (2) preparation joins in the reactor then, wherein step (2) is 1: 2 with the volume ratio of step (3) solution, stirring reaction 12 hours, obtain oyster white or white opacity liquid, centrifugation obtains the colloidal solid of vinylbenzene-Sipacril 2739OF microsphere surface cladding titanium dioxide;
(5) colloidal solid of the vinylbenzene that step (4) is obtained-Sipacril 2739OF microsphere surface cladding titanium dioxide is distributed in the mixing solutions of ethanol and toluene, wherein toluene and alcoholic acid volume ratio are 1: 2, stirred 12 hours, centrifugation obtains the titanium dioxide/vinylbenzene-Sipacril 2739OF microballoon composite particles of homogeneous;
(6) homogeneous titanium dioxide/vinylbenzene that step (5) is obtained-Sipacril 2739OF microballoon composite particles is 450 ℃ of following sintering 2 hours in temperature, obtain monodisperse spherical mesoporous titanium oxide colloid particle, the particle size distribution average deviation is less than 10%, the particulate diameter is 130nm, and specific surface area is between 125m
2/ g.As shown in Figure 1.
Embodiment 2
(1) dehydrated alcohol and the acetone volume ratio by 10: 3 is mixed;
(2) tetrabutyl titanate is dissolved in the mixed solvent of step (1) gained, stirs, wherein the starting point concentration of tetrabutyl titanate is 5 * 10
-4Mol;
(3) ammoniacal liquor is added in the mixed solvent of step (1) gained, stirs, and then to add a certain amount of diameter be that the PSMMA ball of 260nm is uniformly dispersed that wherein the starting point concentration of ammonia is 0.06 mol, the starting point concentration of PSMMA ball is 0.012 grams per liter;
(4) under room temperature (25～30 ℃) condition, the solution of step (3) preparation is joined in the reactor, tetrabutyl titanate mixed solvent solution with step (2) preparation joins in the reactor then, wherein step (2) is 3: 2 with the volume ratio of step (3) solution, stirring reaction 2 hours, obtain oyster white or white opacity liquid, centrifugation obtains the colloidal solid of vinylbenzene-Sipacril 2739OF microsphere surface cladding titanium dioxide;
(5) colloidal solid of the vinylbenzene that step (4) is obtained-Sipacril 2739OF microsphere surface cladding titanium dioxide is distributed in the mixing solutions of ethanol and tetrahydrofuran (THF), wherein tetrahydrofuran (THF) and alcoholic acid volume ratio are 1: 6, stirred 8 hours, centrifugation obtains the titanium dioxide/vinylbenzene-Sipacril 2739OF microballoon composite particles of homogeneous;
(6) homogeneous titanium dioxide/vinylbenzene that step (5) is obtained-Sipacril 2739OF microballoon composite particles is 650 ℃ of following sintering 3 hours in temperature, obtain monodisperse spherical mesoporous titanium oxide colloid particle, the particle size distribution average deviation is less than 10%, the particulate diameter is 143nm, and specific surface area is between 110m
2/ g.
Embodiment 3
(1) dehydrated alcohol and the acetonitrile volume ratio by 1: 13 is mixed;
(2) titanium isopropylate is dissolved in the mixed solvent of step (1) gained, stirs, wherein the starting point concentration of titanium isopropylate is 2.5 * 10
-2Mol;
(3) water is added in the mixed solvent of step (1) gained, stirs, and then the PSMMA ball that to add a certain amount of homemade diameter be 350nm is uniformly dispersed, wherein the starting point concentration of water is 0.1 mol, and the starting point concentration of PSMMA ball is 0.025 grams per liter;
(4) at ambient temperature, the solution of step (3) preparation is joined in the reactor, titanium isopropylate mixed solvent solution with step (2) preparation joins in the reactor then, wherein step (2) is 4: 1 with the volume ratio of step (3) solution, stirring reaction 3 hours, obtain oyster white or white opacity liquid, centrifugation obtains the colloidal solid of vinylbenzene-Sipacril 2739OF microsphere surface cladding titanium dioxide;
(5) colloidal solid of the vinylbenzene that step (4) is obtained-Sipacril 2739OF microsphere surface cladding titanium dioxide is distributed in the mixing solutions of ethanol and toluene, wherein toluene and alcoholic acid volume ratio are 1: 2, stirred 24 hours, centrifugation obtains the titanium dioxide/vinylbenzene-Sipacril 2739OF microballoon composite particles of homogeneous;
(6) homogeneous titanium dioxide/vinylbenzene that step (5) is obtained-Sipacril 2739OF microballoon composite particles is 450 ℃ of following sintering 4 hours in temperature, obtain monodisperse spherical mesoporous titanium oxide colloid particle, the particle size distribution average deviation is less than 10%, the particulate diameter is 162nm, and specific surface area is between 140m
2/ g.
Embodiment 4
(1) dehydrated alcohol and the Virahol volume ratio by 5: 9 is mixed;
(2) tetrabutyl titanate is dissolved in the mixed solvent of step (1) gained, stirs, wherein the starting point concentration of tetrabutyl titanate is 0.125 mol;
(3) ammoniacal liquor is added in the mixed solvent of step (1) gained, stirs, and then the PSMMA ball that to add a certain amount of commercially available diameter be 90nm is uniformly dispersed, wherein the starting point concentration of ammonia is 0.6 mol, and the starting point concentration of PSMMA ball is 0.2 grams per liter;
(4) at ambient temperature, the solution of step (3) preparation is joined in the reactor, tetrabutyl titanate mixed solvent solution with step (2) preparation joins in the reactor then, wherein step (2) is 1: 1 with the volume ratio of step (3) solution, stirring reaction 2 hours, obtain oyster white or white opacity liquid, centrifugation obtains the colloidal solid of vinylbenzene-Sipacril 2739OF microsphere surface cladding titanium dioxide;
(5) colloidal solid of the vinylbenzene that step (4) is obtained-Sipacril 2739OF microsphere surface cladding titanium dioxide is distributed in the mixing solutions of ethanol and tetrahydrofuran (THF), wherein tetrahydrofuran (THF) and alcoholic acid volume ratio are 4: 1, stirred 35 hours, centrifugation obtains the titanium dioxide/vinylbenzene-Sipacril 2739OF microballoon composite particles of homogeneous;
(6) homogeneous titanium dioxide/vinylbenzene that step (5) is obtained-Sipacril 2739OF microballoon composite particles is 400 ℃ of following sintering 2.5 hours in temperature, obtain monodisperse spherical mesoporous titanium oxide colloid particle, the particle size distribution average deviation is less than 10%, the particulate diameter is 45nm, and specific surface area is between 300m
2/ g.
Embodiment 5
(1) dehydrated alcohol and the acetone volume ratio by 14: 2 is mixed;
(2) tetraethyl titanate is dissolved in the mixed solvent of step (1) gained, stirs, wherein the starting point concentration of tetraethyl titanate is 0.5 mol;
(3) ammoniacal liquor is added in the mixed solvent of step (1) gained, stirs, and then to add a certain amount of diameter be that the PSMMA ball of 3200nm is uniformly dispersed that wherein the starting point concentration of ammonia is 3 mol, the starting point concentration of PSMMA ball is 45 grams per liters;
(4) at ambient temperature, the solution of step (3) preparation is joined in the reactor, tetraethyl titanate mixed solvent solution with step (2) preparation joins in the reactor then, wherein step (2) is 1: 4 with the volume ratio of step (3) solution, stirring reaction 7 hours, obtain oyster white or white opacity liquid, centrifugation obtains the colloidal solid of vinylbenzene-Sipacril 2739OF microsphere surface cladding titanium dioxide;
(5) colloidal solid of the vinylbenzene that step (4) is obtained-Sipacril 2739OF microsphere surface cladding titanium dioxide is distributed in the mixing solutions of ethanol and toluene, wherein toluene and alcoholic acid volume ratio are 5: 7, stirred 24 hours, centrifugation obtains the titanium dioxide/vinylbenzene-Sipacril 2739OF microballoon composite particles of homogeneous;
(6) homogeneous titanium dioxide/vinylbenzene that step (5) is obtained-Sipacril 2739OF microballoon composite particles is 600 ℃ of following sintering 2 hours in temperature, obtain monodisperse spherical mesoporous titanium oxide colloid particle, the particle size distribution average deviation is less than 10%, the particulate diameter is 1350nm, and specific surface area is between 85m
2/ g.
Claims (10)
1. the preparation method of the controlled monodisperse spherical mesoporous titanium oxide colloid particle of size and pattern is characterized in that described method may further comprise the steps:
(1) dehydrated alcohol and the polar solvent volume ratio by 1: 15～15: 1 is mixed;
(2) titanic acid ester is dissolved in the mixed solvent of step (1) gained, stirs, wherein the starting point concentration of titanic acid ester is 1 * 10
-4～5 mol;
(3) with water or ammonia solvent in the mixed solvent of step (1) gained, stir, and then adding vinylbenzene-Sipacril 2739OF microballoon is uniformly dispersed, wherein the starting point concentration of ammonia is 0.01～5 mol, the starting point concentration of water is 0.01～5 mol, and the starting point concentration of vinylbenzene-Sipacril 2739OF microballoon is 0.01～100 grams per liter;
(4) at ambient temperature, the solution of step (3) preparation is joined in the reactor, titanic acid ester mixed solvent solution with step (2) preparation joins in the reactor then, wherein step (2) is 1: 5～5: 1 with the volume ratio of step (3) solution, stirring reaction, obtain oyster white or white opacity liquid, centrifugation obtains the colloidal solid of vinylbenzene-Sipacril 2739OF microsphere surface cladding titanium dioxide;
(5) colloidal solid of the vinylbenzene that step (4) is obtained-Sipacril 2739OF microsphere surface cladding titanium dioxide is distributed in the mixing solutions of ethanol and organic solvent, wherein organic solvent and alcoholic acid volume ratio are 1: 9～9: 1, stir, centrifugation obtains the titanium dioxide/vinylbenzene-Sipacril 2739OF microballoon composite particles of homogeneous;
(6) homogeneous titanium dioxide/vinylbenzene that step (5) is obtained-Sipacril 2739OF microballoon composite particles is 350～1000 ℃ of following sintering in temperature, obtains monodisperse spherical mesoporous titanium oxide colloid particle.
2. method according to claim 1 is characterized in that: the distribution of sizes average deviation of described monodisperse spherical mesoporous titanium oxide colloid particle is less than 10%, and the particulate diameter is in 20～2000 nanometers, and specific surface area is between 50～1000m
2/ g.
3. method according to claim 1 is characterized in that: the starting point concentration of described step (2) titanic acid ester is 5 * 10
-4～1.5 mol.
4. method according to claim 1 is characterized in that: the stirring reaction time of described step (4) is 0.5～10 hour.
5. method according to claim 1 is characterized in that: described step (5) churning time is 5～48 hours.
6. method according to claim 1 is characterized in that: described polar solvent is acetone, acetonitrile or Virahol.
7. method according to claim 1 is characterized in that: described step (6) sintering time is 1～5 hour.
8. according to claim 1 or 3 described methods, it is characterized in that: described titanic acid ester molecular formula is [Ti (OR)
4], wherein R is-C
nH
2n+1, n=2～4.
9. method according to claim 1 is characterized in that: described vinylbenzene-Sipacril 2739OF diameter of micro ball is that 30nm is to 5 μ m.
10. method according to claim 1 is characterized in that: described organic solvent is toluene or tetrahydrofuran (THF).
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| CN102139917A (en) * | 2010-12-31 | 2011-08-03 | 昆明冶金高等专科学校 | Preparation method for mesoporous titanium dioxide material |
| CN102367180A (en) * | 2011-03-17 | 2012-03-07 | 中国科学院过程工程研究所 | Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source |
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| CN103570065A (en) * | 2013-10-29 | 2014-02-12 | 台州学院 | Dual-template preparation method of mesoporous TiO2 sphere |
| CN103623798A (en) * | 2013-10-29 | 2014-03-12 | 西南交通大学 | Single-layer mono-dispersed hollow TiO2 microsphere array fixed on Ti substrate |
| CN103623798B (en) * | 2013-10-29 | 2015-05-20 | 西南交通大学 | Single-layer mono-dispersed hollow TiO2 microsphere array fixed on Ti substrate |
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| CN103706347A (en) * | 2013-12-09 | 2014-04-09 | 上海应用技术学院 | TiO2 microsphere and preparation method therefor |
| CN103706347B (en) * | 2013-12-09 | 2015-08-26 | 上海应用技术学院 | A kind of TiO2 microballoon and preparation method thereof |
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