CN104118906B - A kind of method that polymer assistant depositing prepares poriferous titanium dioxide - Google Patents
A kind of method that polymer assistant depositing prepares poriferous titanium dioxide Download PDFInfo
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- CN104118906B CN104118906B CN201410380909.4A CN201410380909A CN104118906B CN 104118906 B CN104118906 B CN 104118906B CN 201410380909 A CN201410380909 A CN 201410380909A CN 104118906 B CN104118906 B CN 104118906B
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Abstract
The present invention relates to a kind of method that polymer assistant depositing prepares poriferous titanium dioxide, step includes the preparation of titanium precursors solution successively, add porogen, heat treatment forms nano titanium dioxide porous material.The present invention adopts water-soluble polymer polymine and derivant thereof to prepare poriferous titanium dioxide as protective agent assistant depositing, has that technique is simple, consume energy the advantage such as little.The poriferous titanium dioxide of preparation has significantly high specific surface area, flourishing orderly pore passage structure, adjustable aperture size in certain limit, and surface is easily modified.
Description
Technical field
The invention belongs to field of nanometer material technology, particularly to a kind of method that polymer assistant depositing prepares poriferous titanium dioxide.
Background technology
Nano material is usually and is made up of the particle of 1～100nm, and it is between the transitional region of macroscopic material and microcosmic atom, molecule, is a kind of typical mesoscopic systems.When small particle size enters nanometer scale, itself it is provided with small-size effect, quantum effect, skin effect and macro quanta tunnel effect etc..Micronization due to particle scale so that nano material shows the special nature different from traditional material, thus mechanical performance, magnetic, optical, electrical, hot etc. in be very different with traditional material.Nano-TiO2Except there is the general characteristic that nanoparticle possesses, also there is the characteristic of semi-conducting material.These characteristics determine it and have huge potential using value, are widely used in many fields such as high-performance coating, ceramic material, ink material, solaode, semi-conducting material, deodorization be antibacterial, air cleaning, sewage disposal.
Nano-TiO2It is divided into non-hole TiO2With porous TiO2.With compared with non-hole TiO2, porous TiO2Having abundant pore passage structure and bigger specific surface area, improving mass-transfer efficiency, increasing surface activity point position, strengthening the absorption of light, shorten photogenerated charge from body to the diffusion length on surface, the many aspects such as separation efficiency improving photogenerated charge have clear superiority.Just because of this, porous TiO2It is widely used in the fields such as light degradation organic pollution, photocatalytic water, photovoltaic solar cell, electroluminescent.
At present, porous TiO2The synthetic method of material is broadly divided into two big classes: template and without templating self-assembly method.Template is divided into again soft template method and hard template method.Wherein, soft template method is to be established the earliest, is also prepare porous TiO2Most common method.Utilize the synthesizing porous TiO of soft template2Model experiment process as follows: (1) by a certain amount of organic formwork agent dissolve in ethanol；(2) TiCl is added4And strong agitation；(3) gained colloidal sol is placed 1-7 days in the open surface ware of 400 DEG C；(4) gained dried powder is calcined 5 hours removal template at 400 DEG C, porous TiO can be obtained2Material.Hard template method is also often used to synthesizing porous TiO2Material, the hard template often used has colloidal carbon sphere, mesoporous silicon oxide and mesoporous carbon etc..Although template synthesis porous TiO2Theory comparison ripe, successful example is also very many.But the method still suffers from deficiency: (1) template is deviate to often result in pore structure and caved in；(2) gained sample is generally low-crystallinity material.Compared with template, fairly simple without templating self-assembly method, cheap, it is thus achieved that material generally also there is higher degree of crystallinity.But, big without templating self-assembly method occasionality, formation mechenism is not clear, it does not have being formed can the theoretical system of foundation.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, it is desirable to provide a kind of method that polymer assistant depositing prepares poriferous titanium dioxide.
A kind of method that polymer assistant depositing prepares poriferous titanium dioxide, including following operating procedure:
Add the water-soluble polymer of the deionized water of mass fraction 70-90%, the titanium tetrachloride of 10-30%, the ethylenediaminetetraacetic acid of 5-30% and 5-30%, regulate pH to 7-7.8, it is uniformly mixing to obtain precursor solution, use the Amicon ultrafiltration system with ultrafilter membrane that precursor solution is carried out ultrafiltration, remove the molecular weight impurity less than 3000g/mol, obtain water solublity coating solution.Apply the porogen adding mass fraction 2-5% in solution to water solublity, stir, obtain the mixed solution containing porogen and titanium.Finally mixed solution is placed in air or pure oxygen atmosphere 450-550 DEG C annealing 2-48h, obtain poriferous titanium dioxide.
Wherein water-soluble polymer is one or more in the polymine of Carboxylation polymine, Sulfonated polymine, acidylate.Porogen is anionic surfactant oleic acid, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, cationic surface active agent benzalkonium chloride, benzalkonium bromide, long carbon chain quaternary ammonium salt, zwitterionic surfactant lecithin, amino acid pattern and betaine type, nonionic surfactant polyalcohols, water miscible poly ion liquid polyvinyl imidazol class, polyvinylpyridine class, one or more in hydrophilic polymer polyvinyl alcohol, Polyethylene Glycol, polystyrolsulfon acid.
There is advantages that
The present invention adopts water-soluble polymer polymine and derivant thereof to prepare poriferous titanium dioxide as protective agent assistant depositing, has the advantages such as technique is simple, easy to operate.The poriferous titanium dioxide of preparation has significantly high specific surface area, flourishing orderly pore passage structure, adjustable aperture size in certain limit, and surface is easily modified, can be applicable to the numerous areas such as high-performance coating, ceramic material, solaode, semi-conducting material, deodorization be antibacterial, air cleaning, sewage disposal.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.
Embodiment 1:
Add the Carboxylation polymine of 70ml deionized water, 10g titanium tetrachloride, 10g ethylenediaminetetraacetic acid and 10g, regulate pH to 7, high-speed stirred mix homogeneously, then solution is carried out ultrafiltration remove the molecular weight impurity less than 3000g/mol obtain water solublity coating solution.Adding 2g sodium lauryl sulphate, stir, being placed in air 450 DEG C of annealing obtains poriferous titanium dioxide in 24 hours.
Embodiment 2:
Add the polymine of 85ml deionized water, 5g titanium tetrachloride, 3g ethylenediaminetetraacetic acid and 7g acidylate, regulate pH to 7.8, high-speed stirred mix homogeneously, then solution is carried out ultrafiltration remove the molecular weight impurity less than 3000g/mol and obtain water solublity coating solution.Adding 4g dodecylbenzene sodium sulfonate, stir, being placed in air 500 DEG C of annealing obtains poriferous titanium dioxide in 12 hours.
Embodiment 3:
Add 90ml deionized water, 3g titanium tetrachloride, 6g ethylenediaminetetraacetic acid and the Sulfonated polymine of 1g, regulate pH to 7.5, high-speed stirred mix homogeneously, then solution is carried out ultrafiltration remove the molecular weight impurity less than 3000g/mol and obtain water solublity coating solution.Adding 3g benzalkonium bromide, stir, being placed in air 550 DEG C of annealing obtains poriferous titanium dioxide in 36 hours.
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot all of embodiment be given exhaustive.Every belong to apparent change that technical scheme amplified out or the variation row still in protection scope of the present invention.
Claims (2)
1. the method that a polymer assistant depositing prepares poriferous titanium dioxide, it is characterised in that described polymer assistant depositing is prepared the method for poriferous titanium dioxide and comprised the following steps: successively to prepare titanium precursors solution, ultrafiltration, interpolation porogen, heat treatment:
Step 1: add the water-soluble polymer of the deionized water of mass fraction 70-90%, the titanium tetrachloride of 10-30%, the ethylenediaminetetraacetic acid of 5-30% and 5-30%, regulates pH to 7-7.8, is uniformly mixing to obtain precursor solution；
Wherein said deionized water, titanium tetrachloride, ethylenediaminetetraacetic acid, water-soluble copolymer component content sum are 100%,
Described water-soluble polymer is one or more in the polymine of Carboxylation polymine, Sulfonated polymine, acidylate；
Step 2: use the Amicon ultrafiltration system with ultrafilter membrane that the precursor solution described in step 1 carries out ultrafiltration, remove the molecular weight impurity less than 3000g/mol, obtains water solublity coating solution；
Step 3: add the porogen of mass fraction 2-5% in the water solublity coating solution that step 2 obtains, stir, obtain the mixed solution containing porogen and titanium；
Step 4: mixed solution step 3 obtained is placed in air or pure oxygen atmosphere, anneals 2-48 hour, obtains poriferous titanium dioxide for 450-550 DEG C.
2. the method that polymer assistant depositing according to claim 1 prepares poriferous titanium dioxide, it is characterized in that: porogen described in step 3 is anionic surfactant oleic acid, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, cationic surface active agent benzalkonium chloride, benzalkonium bromide, long carbon chain quaternary ammonium salt, zwitterionic surfactant lecithin, amino acid pattern and betaine type, nonionic surfactant polyalcohols, water miscible poly ion liquid polyvinyl imidazol class, polyvinylpyridine class, hydrophilic polymer polyvinyl alcohol, Polyethylene Glycol, one or more in polystyrolsulfon acid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844806A (en) * | 2010-06-09 | 2010-09-29 | 华南师范大学 | Method for ethylene diamine tetraacetic acid (EDTA)-assisted hydrothermal synthesis of nanometer porous titanium dioxide(TiO2) |
| CN102502810A (en) * | 2011-11-01 | 2012-06-20 | 南京林业大学 | Method for preparing porous nano TiO2 |
| CN103601237A (en) * | 2013-11-06 | 2014-02-26 | 北京工业大学 | Charged anatase titania nanoparticles and low-temperature preparation method thereof |
| CN103949232A (en) * | 2014-04-30 | 2014-07-30 | 上海师范大学 | TiO2 photocatalyst with mesoporous structure, as well as preparation method and applications of photocatalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844806A (en) * | 2010-06-09 | 2010-09-29 | 华南师范大学 | Method for ethylene diamine tetraacetic acid (EDTA)-assisted hydrothermal synthesis of nanometer porous titanium dioxide(TiO2) |
| CN102502810A (en) * | 2011-11-01 | 2012-06-20 | 南京林业大学 | Method for preparing porous nano TiO2 |
| CN103601237A (en) * | 2013-11-06 | 2014-02-26 | 北京工业大学 | Charged anatase titania nanoparticles and low-temperature preparation method thereof |
| CN103949232A (en) * | 2014-04-30 | 2014-07-30 | 上海师范大学 | TiO2 photocatalyst with mesoporous structure, as well as preparation method and applications of photocatalyst |
Non-Patent Citations (1)
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| Single-walled carbon nanotubes coated with titania nanoparticles;Jing Sun et al.;《Carbon》;20041231;第42卷;第895-899页 * |
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