CN104588118A - Titanium oxide photocatalyst and preparation method thereof - Google Patents
Titanium oxide photocatalyst and preparation method thereof Download PDFInfo
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- CN104588118A CN104588118A CN201310529479.3A CN201310529479A CN104588118A CN 104588118 A CN104588118 A CN 104588118A CN 201310529479 A CN201310529479 A CN 201310529479A CN 104588118 A CN104588118 A CN 104588118A
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Abstract
The invention discloses a preparation method of a titanium oxide photocatalyst. The method comprises the following steps: 1, adding a divinyl benzene monomer, an initiator and a titanium compound to an organic solvent, stirring for 30-90min, adding the obtained mixture to a hydrothermal synthesis reaction kettle, and carrying out a polymerization reaction at 140-180DEG C for 24-36h; 2, opening the hydrothermal synthesis reaction kettle after the polymerization reaction carried out in step 1, adding an acidic solution, and carrying out heat treatment at 200-300DEG C for 24-48h; and 3, taking out the obtained compound solid after the heat treatment carried out in step 2, and drying the compound solid to obtain the TiO2-mesoporous polydivinyl benzene photocatalyst. The pollutant degradation effect of the TiO2-mesoporous polydivinyl benzene photocatalyst prepared through the method is greatly improved.
Description
Technical field
The invention belongs to photocatalysis technology field, particularly a kind of oxide of high activity titanium photochemical catalyst and preparation method thereof.
Background technology
As novel high-level oxidation technology, photocatalytic oxidation has become Disciplinary Frontiers and the study hotspot of environmental improvement.Photochemical catalytic oxidation is utilized to be expected to realize organic degree of depth mineralising.TiO
2the most frequently used photochemical catalyst, TiO
2two kinds can be divided in the reactor: floating type and support type.Floating type has good dispersion, and specific area is large, reaction efficiency high.Particularly nano-TiO
2, not only specific area is large, and the scale effect of its uniqueness is of great benefit to wastewater degradation.Although floating type TiO
2there is higher degradation efficiency, but be difficult to after the reaction be separated, not only affect effluent quality, and need constantly to supplement TiO along with the prolongation in reaction time
2, cause the increase of financial cost.By TiO
2photocatalyst, on mesoporous adsorption material, not only can realize the function to reactant enrichment, promotes the generation of catalytic reaction, and is conducive to TiO
2the recovery of catalyst and recycling, make it more stable.
The PDVB material of meso-hole structure is as the one of polymeric adsorbent, and having excellent hydrophobicity and the material of characterization of adsorption, is load TiO
2the ideal material of catalyst.But mesoporous polyvinylidene base benzene synthetic method is loaded down with trivial details, much carries out all in aqueous, and the predecessor tetrabutyl titanate, titanium tetrachloride etc. of titanium dioxide are all easy to hydrolysis, very high to the requirement of solvent, so, screen suitable TiO
2the method of-mesoporous polyvinylidene base benzene materials synthesis is very difficult.
Forever the use hydrothermal synthesis method such as (solvent-thermally synthesizing nano pore polymer and adsorption function research thereof, Jilin University Ph.D. Dissertation, 2009), successfully synthesizes TiO first
2-mesoporous polyvinylidene base benzene material, its preparation method is as follows: first, is dissolved in 10 milliliters of oxolanes by 2 grams of divinylbenzene monomers, adds the butyl titanate of different amount subsequently.To be mixed evenly after, add the azodiisobutyronitrile (AIBN) of 0.05 gram as polymerization initiator.This mixture at room temperature stirs 4 hours, is moved into subsequently in reactor and leaves standstill 1 day in 100 DEG C of baking ovens.Naturally cooled by reactor and open, then the water adding 10 milliliters put into 100 DEG C of baking ovens and placed 1 day, and 180 DEG C of baking ovens place one day, and then still is driven in room temperature cooling, vapors away liquid flux, dries the product namely obtained.Although this material has abundant pore passage structure, in the application process of reality, photocatalysis effect is undesirable all the time, significantly limit TiO
2the application of-mesoporous polyvinylidene base benzene in degradation of contaminant.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of titania photocatalyst and preparation method thereof.TiO prepared by the method
2the effect of-mesoporous polyvinylidene base benzene photochemical catalyst in degradation of contaminant is greatly improved.
A preparation method for titania photocatalyst, comprises the steps:
(1) in organic solvent, add divinylbenzene monomers, initator, titanium compound, stir and to load in hydrothermal synthesis reaction still polymerisation 24-36h at 140-180 DEG C after 30-90min;
(2) step (1) polymerisation is fetched boiling water after terminating thermal synthesis reactor, adds acid solution and process 24-48h at 200-300 DEG C;
(3), after step (2) heat treatment terminates, composite solids obtained TiO is after drying taken out
2-mesoporous polyvinylidene base benzene photochemical catalyst.
The inventive method, in step (1) polymerization system, the mass content of divinylbenzene monomers is 70%-85%, and the mass content of titanium compound is 15%-30%.Described initator is one or more in methyl isobutyrate of 2,2-azo two itrile group valeric acid, ABVN or azo two.Described titanium compound comprises titanium tetrachloride, butyl titanate, preferred titanium tetrachloride.
The inventive method, organic solvent described in step (1) is one or more in oxolane, dioxane, acetone, ethanol, acetonitrile, methyl alcohol and dimethyl formamide, the mixed solvent of preferred acetone, methyl alcohol and dimethyl formamide, the volume fraction of acetone, methyl alcohol and dimethyl formamide is respectively 40 ~ 50%, 20 ~ 35%, 20 ~ 30%.Adopt TiO prepared by the mixed solvent of acetone, methyl alcohol and dimethyl formamide
2without the organic solvent that absorption is residual in-mesoporous polyvinylidene base benzene photochemical catalyst, further increase photocatalytic degradation effect.
The inventive method, the acid solution added in step (2) comprises sulfuric acid solution, salpeter solution, hydrochloric acid solution etc.The molar concentration of acid solution is 0.001-0.2mol/L, adds 1-3 times that volume is organic solvent volume in step 1.
The inventive method, the drying described in step (2) is vacuum drying, and baking temperature is 60-120 DEG C, and drying time is 1-20h, and preferred baking temperature is 70-100 DEG C, and drying time is 4-10h.
Adopt a titania photocatalyst prepared by above method, specific area is 244-449m
2/ g, aperture is 15-35nm, and in catalyst, the weight content of titanium oxide is 5% ~ 20%, and in catalyst, the mol ratio of Detitanium-ore-type and rutile is 2:1-5:1.
The absorption that the present invention obtains-degraded dual functional polymer material has strong hydrophobic oleophilic oil, and to some large molecular organic pollutants, such as rhodamine, toluene, ortho-xylene, petrol and diesel oil etc. show superpower adsorption capacity.Present invention efficiently solves in photochemical catalyst use procedure the difficult problem being difficult to reclaim, and pollutant can be concentrated degraded, building-up process is simple, and cost is low, has broad application prospects in the improvement of low concentration wastewater and VOCs.
Result of study shows, the TiO prepared in prior art
2-main cause that mesoporous polyvinylidene base benzene photochemical catalyst photocatalysis efficiency is low is TiO
2crystal formation organic solvent that is single and the mesoporous polyvinylidene base benzene absorption with strong absorption property be difficult to remove completely.TiO prepared by the inventive method
2-mesoporous polyvinylidene base benzene photochemical catalyst effectively can control the crystalline structure of titanium dioxide, prepares the nano titanium oxide crystal grain that rutile-type, both Detitanium-ore-types with proper proportion mixes, improves the catalytic effect of photochemical catalyst.
Accompanying drawing explanation
The XRD spectra of Fig. 1 sample prepared by embodiment 3.
Detailed description of the invention
Further illustrate process and the effect of the inventive method below in conjunction with embodiment and comparative example, but following examples do not form the restriction to the inventive method.
Embodiment 1
4.0g divinylbenzene monomers is added in the mixed solvent of 15g acetone, methyl alcohol and dimethyl formamide (three's volume ratio is 50:20:30), add 0.05g 2, the two itrile group valeric acid initator (for 1% of divinylbenzene quality) of 2-azo, add 1.4g titanium tetrachloride again, stirring at room temperature 60min, loads hydrothermal synthesis reaction still; Polymerisation 24h at 180 DEG C, obtains block composite solids.To fetch boiling water thermal synthesis reactor, add the sulfuric acid solution of 0.0015mol/L, add 2 times that volume is acetone, methyl alcohol and dimethyl formamide mixed solvent volume, 240 DEG C of hydrothermal treatment consists 36h, after reaction stops, take out solid sample, put into heating in vacuum (80 DEG C) dry 10h, remove organic solvent, block polymeric material can be obtained, wherein titanium dioxide mass fraction is 13%, and recording its specific area is 423 m
2/ g, aperture is at 35 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about 1:5.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution is 21 mg/L.
Embodiment 2
According to the method preparation in embodiment 1, only change solvent acetone, methyl alcohol and dimethyl formamide (three's volume ratio is 45:35:20) ratio; Can obtain block polymeric material, wherein titanium dioxide mass fraction is 13%, and recording its specific area is 355 m
2/ g, aperture is at 21 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about two kinds of crystal formation ratios and are about 2:3.Put in the rhodamine B solution of 50mg/L according to embodiment 1 by sample, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution is 18mg/L.
embodiment 3
According to the method preparation in embodiment 1, only change solvent acetone, methyl alcohol and dimethyl formamide (three's volume ratio is 40:35:25) ratio; Can obtain block polymeric material, wherein titanium dioxide mass fraction is 13%, and recording its specific area is 449 m
2/ g, aperture is at 21 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about two kinds of crystal formation ratios and are about 1:3.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution reduces to 5 mg/L.
Embodiment 4
Prepare sample according to the method in embodiment 3, the concentration only changing sulfuric acid solution is 0.15mol/L; Can obtain block polymeric material, wherein titanium dioxide mass fraction is 13%, and recording its specific area is 433 m
2/ g, aperture is at 20 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about two kinds of crystal formation ratios and are about 1:5.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution reduces to 10 mg/L.
Embodiment 5
Prepare sample according to the method in embodiment 3, acetone, methyl alcohol and dimethyl formamide mixed solvent are become oxolane, can obtain block polymeric material, wherein titanium dioxide mass fraction is 13%, and recording its specific area is 458 m
2/ g, aperture is at 23 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about two kinds of crystal formation ratios and are about 1:3.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution reduces to 78mg/L.
Embodiment 6
Prepare sample according to the method in embodiment 3, acetone, methyl alcohol and dimethyl formamide mixed solvent are become acetone, can obtain block polymeric material, wherein titanium dioxide mass fraction is 13%, and recording its specific area is 449 m
2/ g, aperture is at 22 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about two kinds of crystal formation ratios and are about 1:3.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution reduces to 115mg/L.
Embodiment 7
Prepare sample according to the method in embodiment 3, only change TiCl
4quality be 0.9g; Can obtain block polymeric material, wherein titanium dioxide mass fraction is 8.5%, and recording its specific area is 425 m
2/ g, aperture is at 20 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about two kinds of crystal formation ratios and are about 1:4.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution reduces to 10mg/L.
Embodiment 8
Prepare sample according to the method in embodiment 3, only change TiCl
4volume be 1.5g; Can obtain block polymeric material, wherein titanium dioxide mass fraction is 18%, and recording its specific area is 435 m
2/ g, aperture is at 19 ran, and XRD test shows, rutile and anatase two kinds of crystal formation ratios are about two kinds of crystal formation ratios and are about 1:2.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution reduces to 23mg/L.
Comparative example 1
According to the method preparation in embodiment 1, just acid solution is changed to isopyknic aqueous solution.Can obtain block polymeric material, recording its specific area is 546 m
2/ g, aperture is at 15 ran, and XRD test shows, titanium dioxide is all Detitanium-ore-type.Get this sample of 50mg, put into the rhodamine B solution of 2ml 50mg/L, irradiate 2h under the xenon lamp of 500W after, the COD value of rhodamine B solution is for being 986mg/L.
Claims (11)
1. a preparation method for titania photocatalyst, is characterized in that: comprise the steps:
(1) in organic solvent, divinylbenzene monomers, initator, titanium compound is added, polymerisation 24-36h at 140-180 DEG C in stirring rear loading hydrothermal synthesis reaction still;
(2) step (1) polymerisation is fetched boiling water after terminating thermal synthesis reactor, adds acid solution and process 24-48h at 200-300 DEG C;
(3), after step (2) heat treatment terminates, composite solids obtained TiO is after drying taken out
2-mesoporous polyvinylidene base benzene photochemical catalyst.
2. method according to claim 1, is characterized in that: described in step (1), mixing time is 30-90min.
3. method according to claim 1, is characterized in that: in step (1) polymerization system, the mass content of divinylbenzene monomers is 70%-85%, and the mass content of titanium compound is 15%-30%.
4. method according to claim 1, is characterized in that: described initator is one or more in methyl isobutyrate of 2,2-azo two itrile group valeric acid, ABVN or azo two.
5. method according to claim 1, is characterized in that: described titanium compound comprises titanium tetrachloride, butyl titanate, preferred titanium tetrachloride.
6. method according to claim 1, is characterized in that: the organic solvent described in step (1) is one or more in oxolane, dioxane, acetone, ethanol, acetonitrile, methyl alcohol and dimethyl formamide.
7. method according to claim 1, it is characterized in that: the organic solvent described in step (1) is the mixed solvent for acetone, methyl alcohol and dimethyl formamide, the volume fraction of acetone, methyl alcohol and dimethyl formamide is respectively 40 ~ 50%, and 20 ~ 35%, 20 ~ 30%.
8. method according to claim 1, is characterized in that: the acid solution added in step (2) comprises sulfuric acid solution, salpeter solution, hydrochloric acid solution etc.
9. the method according to claim 1 or 8, is characterized in that: the molar concentration of acid solution is 0.001-0.2mol/L, adds 1-3 times that volume is organic solvent volume in step 1.
10. method according to claim 1, is characterized in that: the drying described in step (2) is vacuum drying, and baking temperature is 60-120 DEG C, and drying time is 1-20h, and preferred baking temperature is 70-100 DEG C, and drying time is 4-10h.
11. 1 kinds of titania photocatalysts adopting claim 1-10 either method to prepare, is characterized in that: specific area is 244-449m
2/ g, aperture is 15-35nm, and in catalyst, the weight content of titanium oxide is 5% ~ 20%, and in catalyst, the mol ratio of Detitanium-ore-type and rutile is 2:1-5:1.
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| WO2011086567A1 (en) * | 2010-01-12 | 2011-07-21 | Council Of Scientific & Industrial Research | Magnetic dye-adsorbent catalyst |
| CN103041866A (en) * | 2013-01-18 | 2013-04-17 | 绍兴文理学院 | Preparation method of titanium dioxide-mesoporous polymer nano porous composite visible light catalytic material |
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| WO2011086567A1 (en) * | 2010-01-12 | 2011-07-21 | Council Of Scientific & Industrial Research | Magnetic dye-adsorbent catalyst |
| CN103041866A (en) * | 2013-01-18 | 2013-04-17 | 绍兴文理学院 | Preparation method of titanium dioxide-mesoporous polymer nano porous composite visible light catalytic material |
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| CN104998690A (en) * | 2015-06-28 | 2015-10-28 | 渤海大学 | Preparation method of composite titanium dioxide nanoparticles |
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