CN104759273A - Preparation method for in-situ carbon doped hollow titanium dioxide visible light photocatalyst - Google Patents
Preparation method for in-situ carbon doped hollow titanium dioxide visible light photocatalyst Download PDFInfo
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- CN104759273A CN104759273A CN201510095295.XA CN201510095295A CN104759273A CN 104759273 A CN104759273 A CN 104759273A CN 201510095295 A CN201510095295 A CN 201510095295A CN 104759273 A CN104759273 A CN 104759273A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to titanium dioxide photocatalysts, especially to a preparation method of an in-situ carbon doped hollow titanium dioxide photocatalyst and application of the photocatalyst in sewage treatment. In order to solve the disadvantage of needing to add a carbon precursor in existing preparation methods for carbon doped titanium dioxide, the invention provides a technology for in-situ preparation of the carbon doped hollow titanium dioxide visible light photocatalyst through carbonization of a cation template. The efficient carbon doped visible light photocatalyst is mainly obtained by control of monodispersion of the cation template, self-assembly of tetrabutyl titanate (TBT) on the template surface, catalytic hydrolysis of TBT and segmented programmed calcination to remove the template. Therefore, the method provided by the invention is continuation and further expansion of the titanium dioxide preparation technology, and is also invented directed at the disadvantages of slow reaction rate, low quantization yield, poor solar energy utilization ability and the like. And the research result can be widely applied to atmospheric pollution, wastewater treatment, solar cell development and other fields.
Description
Technical field
The present invention relates to titanium dioxide optical catalyst, refer in particular to the preparation method of hollow titanium dioxide photochemical catalyst and the application in sewage disposal thereof of the doping of a kind of in-situ carbon.
Background technology
A large amount of industry, agricultural and domestic pollutant enter in the middle of environment, cause serious water pollution, these pollutants there is health (the L. Jing that human body in serious threat, W. Zhou, G. Tian, H. Fu. Surface tuning for oxide-based nanomaterials as efficient photocatalysts.
chem.
soc.
rev.,
2013,
42, 9509), therefore, how effectively to remove these pollutants, just become one of study hotspot of current environmental science; Compare with biological prosthetic with physical absorption, photocatalytic degradation is as a kind of green technology, the degradable all contaminants of energy, and any toxic pollutant or intermediate can not be produced, be considered to the most desirable and the most promising depollution of environment technology (the W. J. Ong of one, L. Tan, S. P. Chai, S. T. Yong. Facet-dependent photocatalytic properties of TiO2-based composites for energy conversion and environmental remediation.
chemSusChem.
2014;
7, 690).
Titanium dioxide has nontoxic, low cost, the efficiently advantage such as ultraviolet catalytic ability and high stability, makes it be widely used in the process field such as atmosphere pollution, contaminated waste water, 1972, A. Fujishima and K. Honda (A. Fujishima, K. Honda, Electrochmeical photolysis of water at a semiconductor electrode.
nature,
1972,
238, 37) since carrying out the research of titanium-dioxide photo decomposition water first, explosive growth is achieved in fields such as the various highly efficient titania photocatalysis apparatus of preparation, and become research topic the most fast such as field of Environment Protection development such as process atmosphere pollution and purification of waste water etc., regrettably, be that photochemical catalyst also also exists following deficiency with titanium dioxide: reaction rate is slow, quantization productive rate is low, utilize the ability of solar energy poor and for shortcomings such as the visible light part utilization rate in sunshine are very low, for this reason, the visible light catalytic effect how improving titanium dioxide just becomes Research Challenges (the A. Ayati of environment protection catalytic new material, A. Ahmadpour, F. Bamoharram, B. Tanhaei, M. Manttari, M. Sillanpaa. A review on catalytic applications of Au/TiO
2nanoparticles in the removal of water pollutant.
chemosphere,
2014,
107, 163).
As everyone knows, the electron-hole that effectively can extend titanium dioxide due to alloy is separated, therefore, by doping metals or the nonmetal visible light catalytic efficiency that can improve titanium dioxide significantly, metal-doped because of its low heat endurance, photoetch and easily become the center of reassociating, and be subject to certain restrictions; By comparison, the visible light catalytic aspect of performance that nonmetal doping is improving titanium dioxide achieves larger success (P. Zhang, C. Shao, Z. Zhang, M. Zhang, J. Mu, Z. Guo, Y. Liu. TiO2@carbon core/shell nanofibers:Controllable preparation and enhanced visible photocatalytic properties.
nanoscale,
2011, 3,2943).
Carbon doping is similar to the photoelectron-a series of advantage such as hole separation and wide visible absorption of the conductive performance of metal, large electron storage capacity, raising because having, and cause very big concern (the S. Lee of scientific worker, Y. Lee, D. H. Kim, J. Moon. Carbon-deposited TiO2 3D inverse opal photocatalysts:visible-light photocatalytic activity and enhanced activity in a viscous solution.
aCSAppl.
mater.
interfaces,
2013,
5, 12526), but, the method preparing now carbon doping titanium dioxide still has very large deficiency, the carbon component adding extra carbon matrix precursor and doping as needed such as easily to assemble at shortcoming (the L. Quan, Y. Jang, K. Stoerzinger, K. May, Y. Jang, S. Kochuveedu, Y. S. Horn, D. H. Kim. Soft-template-carbonization route to highly textured mesoporous carbon – TiO2 inverse opals for efficient photocatalytic and photoelectrochemical applications.
phys. Chem. Chem. Phys.,
2014,
16, 9023), therefore, develop a kind of easy, with low cost method preparing carbon doping titanium dioxide visible light catalyzer, not only there is important theory meaning, more have great using value, starting point of the present invention is just this.In order to realize this target, a kind of cation polystyrene that the present invention adopts inventor to create is template (Chinese invention patent: ZL 200910234354.1), take ethanol as polymerization system, take butyl titanate as titanium precursors, by system research cation template and the interaction mechanism of titanium precursors, the minimizing technology of cation template and titanium dioxide from amorphous to the basis of the mechanism of crystalline transformation, have successfully been obtained the best experimental formula of the hollow titanium dioxide visible light catalyst of in-situ preparation of carbon doping.
Summary of the invention
Task of the present invention is the simple method for preparing of the hollow titanium dioxide environmental friendly material finding a kind of carbon doping, it not only can overcome the existing shortcoming prepared carbon doping titanium dioxide and need additionally to add carbon matrix precursor effectively, and greatly can also promote the visible light catalytic efficiency of titanium dioxide.
For realizing target of the present invention, the present invention adopts the cation polystyrene particle (PS) of monodispersity to be template, take ethanol as solution system, and with butyl titanate (TBT) for titanium precursors, deionized water is catalyst; The temperature controlling reaction system with ice-water bath is 0 DEG C, the ethanolic solution of butyl titanate is slowly added drop-wise in reaction system, after sedimentation a period of time, hydrolysis is carried out after dripping the mixed liquor of appropriate deionized water and ethanol, reaction terminates, sample is carried out centrifugal, washing, dry, again calcining remove cation polystyrene template, original position prepares the hollow titanium dioxide visible light catalyst of carbon doping.
The ethanolic solution of the mixture that reaction system refers to the cation polystyrene particle of monodispersity and ethanol PS template in other words.
Here is to detailed introduction of the present invention:
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, is characterized in that can two factors determine realize in-situ carbon doping: one is the successful preparation of monodisperse cation polystyrene microsphere; Two is how to control the removal of cation template and the crystal phase transition process of titanium dioxide.
The cation polystyrene template that the present invention is used, this template has good monodispersity, this is the prerequisite of the hollow titanium dioxide microballoon of preparation height, preparation method, with reference to Chinese invention patent: ZL 200910234354.1, is characterized in that: cation benzyl vinyl trimethyl ammonium chloride (VTC) monomer added and the mass ratio of styrene monomer are 10%-40%; This is because carrying out self assembly in tetrabutyl titanate hydrolysis thing can at template surface, depend on the electrostatic attraction of TBT hydrolysate and cation template completely, that is, only have when this electrostatic attraction is enough strong, effectively could realize the self assembly of TBT hydrolysate at template surface, and effectively reduce and even prevent TBT hydrolysate to be self-assembled into nano particle; Otherwise, if this electrostatic force more weak (also namely the addition of VTC monomer is inadequate), so guarantee that TBT hydrolysate can wrap up cation template fast, evenly, fully by being difficult to, and TBT also cannot be avoided to be hydrolyzed self assembly nucleation.
The present invention's cation benzyl vinyl trimethyl ammonium chloride (VTC) monomer used is the solid of commercially available mass concentration 99%, be analyze pure, by sigma-aldrich company of the U.S. is produced.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, is characterized in that: the tetra-n-butyl titanate (TBT) used is Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, is characterized in that used TBT needs to dissolve with ethanol in advance, and then slowly drips; The ethanol solution concentration of positive four butyl esters of metatitanic acid that described reaction adopts is at 0.025 ~ 0.2 g/mL, and concentration range can be used for the shell thickness of TIO2, and concentration is larger, and shell thickness is thicker.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, it is characterized in that before deionized water catalyst adds, TBT must be allowed to have the sufficient sedimentation time in cation template, is 24h; Its objective is and make TBT can carry out uniform sedimentation at template surface, add at water and fashionablely can realize " original position " at template surface and be hydrolyzed self assembly, if the sedimentation time is too short, TBT is uneven in template surface sedimentation, and TBT hydrolysis rate is exceedingly fast, finally cause the dispersiveness of the hollow titanium dioxide prepared too poor.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, it is characterized in that: the catalyst deionized water as hydrolysis TBT is no more than 5% of total solvent volume, must under stirring and add with the form of mixtures of water and ethanol, wherein deionized water and ethanol volume ratio 1:2; As directly added water, local can be caused to be hydrolyzed excessive velocities, to cause the reunion that microballoon is a large amount of.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, is characterized in that the PS/TiO to preparation
2the method for calcinating of nucleocapsid structure is that segmented program heats up, because cation template just can start to decompose at about 200 DEG C, and TiO
2from amorphous to anatase crystal phase transition temperature about about 300 DEG C, and just likely to change completely to 500 DEG C; In order to ensure TiO
2before being transformed into anatase crystal completely, template can not be removed completely, and it is best that effect calcined by fire door under buttoned-up status, to ensure TiO
2carbon in crystal phase transition process exists.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, it is characterized in that calcine by steps program is as follows: 25 DEG C are warming up to 250 DEG C, used time 250 min, keeps 60 min; 250 DEG C are warming up to 300 DEG C, and used time 100 min, keeps 30 min; 300 DEG C are warming up to 350 DEG C, and used time 200 min, keeps 120 min; 350 DEG C are warming up to 400 DEG C, and used time 200 min, keeps 60 min; 400 DEG C are warming up to 450 DEG C, and used time 200 min, keeps 120 min.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, it is characterized in that the carbon source of carbon doping hollow titanium dioxide comes from cation template, also namely do not need additionally to add any carbon source, thus original position prepares the hollow titanium dioxide visible light catalyst of carbon doping.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, is characterized in that the shell thickness of hollow titanium dioxide regulates by the addition of TBT.
The preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst of the present invention, it is characterized in that prepared catalyst has very strong visible ray absorption, within 30 minutes, completely rhodamine B can be resolved into intermediate, water and carbon dioxide, and commercially available P25 TiO
2powder only degrades about 60%, also just the rhodamine B of about 90% is resolved into intermediate, water and carbon dioxide after 60 minutes.
The ethanol solution concentration of PS template of the present invention is at 0.025 ~ 0.125 g/mL.
The reaction temperature of described reaction system controls at 0 DEG C.
The sedimentation time of described reaction is 24 h; Hydrolysis time is 20 ~ 25 h.
The washing methods of described product is for alternately cleaning with deionized water and absolute ethyl alcohol.
The baking temperature of described reaction is 60 DEG C, and drying time is 10 ~ 15 h.
The mass ratio of the cation polystyrene particle of described butyl titanate and monodispersity is: 2-5:4.
What described reaction was obtained is the titania-doped microballoon of in-situ carbon, good dispersion, and pattern rule, particle size is mainly distributed in 450 ~ 550 nm.
The present invention, compared with the existing method preparing carbon doping titanium dioxide microballoon sphere, has following outstanding advantage:
(1). it is a kind of monodispersity by controlling cation template, TBT sedimentation and catalyzing hydrolysis speed, realizes its even self assembly at cation template surface, prepares the preparation method of high degree of monodispersity hollow titanium dioxide microballoon.
(2). it is a kind of hollow titanium dioxide microballoon, because it combines the two-fold advantage of hollow material and titanium dioxide, can improve photocatalysis contact rate and adsorb the low thing of more catalysis, and cause the preparation method of higher photocatalysis efficiency.
(3). it is the key factor such as a kind of sedimentation time by accuracy controlling TBT and catalyst system and catalyzing, carrys out the method for control TBT hydrolysis in quick, the even self assembly speed of template surface.
(4). it is a kind of method accurately utilizing segmented program intensification to prepare carbon doping hollow titanium dioxide microballoon.
(5). it a kind ofly utilizes cation template own to provide the method for carbon doping hollow titanium dioxide carbon source.
(6). it is that one does not need additionally to add any carbon source, and the preparation method of in-situ accomplishes carbon doping hollow titanium dioxide.
(7). it is a kind of addition that simply can utilize TBT, realizes carbon doping hollow titanium dioxide shell thickness regulate and control method.
(8). it is a kind of preparation method with the carbon doping hollow titanium dioxide photochemical catalyst of high visible catalytic efficiency.
The carbon doping hollow titanium dioxide photochemical catalyst of preparation of the present invention, it not only has the advantages such as high stability, strong anti-light corrosive power, cost be low and nontoxic, also there is efficient visible light catalysis activity, can the field such as applied environment pollution plot and solar cell widely.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope TEM photo of monodisperse cation polystyrene moulding prepared by embodiment one emulsifier-free emulsion polymerization, method by embodiment one is described, monodisperse particles being prepared, creating conditions for developing orderly carbon doping hollow titanium dioxide.
Fig. 2 is in embodiment one, with monodisperse cation polystyrene for template, and the PS/TiO of preparation
2the transmission electron microscope SEM photo of nucleocapsid structure particle, mainly proves that butyl titanate can carry out uniform self assembly at cationic template surface.
Fig. 3 is with in embodiment one, take cation polystyrene as template, butyl titanate addition is 2 grams, prepared shell thickness is about 20 nanometers, the transmission electron microscope TEM photo of the carbon doping hollow titanium dioxide microballoon of height, when illustrating that the amount adding TBT is 2 grams, the hollow titanium dioxide that more perfect shell thickness is about 20nm can be obtained.
Fig. 4 is with in embodiment two, take cation polystyrene as template, butyl titanate addition is 3 grams, prepared shell thickness is about 29 nanometers, the transmission electron microscope SEM photo of the carbon doping hollow titanium dioxide microballoon of height, when illustrating that the amount adding TBT is 3 grams, the hollow titanium dioxide that more perfect shell thickness is about 29nm can be obtained.
Fig. 5 is with in embodiment three, take cation polystyrene as template, butyl titanate addition is 4 grams, prepared shell thickness is about 41 nanometers, the transmission electron microscope SEM photo of the carbon doping hollow titanium dioxide microballoon of height, when illustrating that the amount adding TBT is 4 grams, the hollow titanium dioxide that more perfect shell thickness is about 45nm can be obtained.
Fig. 6 is with in embodiment four, take cation polystyrene as template, butyl titanate addition is 5 grams, prepared shell thickness is about 59 nanometers, the transmission electron microscope SEM photo of the carbon doping hollow titanium dioxide microballoon of height, when illustrating that the amount adding TBT is 5 grams, the hollow titanium dioxide that more perfect shell thickness is about 59nm can be obtained.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but not limit the scope of the invention;
Embodiment one
The potassium peroxydisulfate of the deionized water of 72g, 8g styrene and 0.16g is put into the four-necked bottle of 150ml, under the state of low whipping speed 350rpm, logical nitrogen removes air, after about 20 minutes, pour in water bath with thermostatic control rapidly with the about 70 DEG C of warm water mixed up in advance, and keep 70 DEG C constant; In reaction after 1.5 hours, under nitrogen protection, with microsyringe, the mixed liquor (with the volume ratio 1:1 of deionized water) of 1.2 g VTC and deionized water is injected reaction bulb, first three pin pin per half an hour one (every pin 10 μ l), after inject two pins again, each hour one pin, every pin is (50 μ l); Surplus solution every 3 minutes injection one pins more subsequently, every pin is (10 μ l), measure until injected all remaining VTC, to be injected complete after, make polymerization extend about 12 hours again, make it fully be polymerized, after being polymerized, use miillpore filter (0.22 μm) carries out suction filtration, washing to polymer and is separated, and finally prepares the cation sub-micron polystyrene moulding of the monodispersity of VTC about 15% (with styrene mass ratio).
Embodiment two
Prepare the hollow titanium dioxide microballoon that shell thickness is about the carbon doping of 20 nm: in 100 mL there-necked flasks, add PS template and 40 mL ethanol that 4 g removed deionized water, magnetic agitation is even, control the temperature of reaction system at 0 DEG C, by 20 mL prepared, the positive four butyl ester ethanolic solutions of metatitanic acid of 0.1 g/mL are slowly added drop-wise to reaction system, after sedimentation 24h, hydrolysis 20h is carried out after mixed (amount of water can not be too high, otherwise TBT hydrolysis rate is too fast) conjunction liquid of slow dropping 3mL deionized water and 6mL ethanol; Reaction terminates, and is undertaken centrifugal by sample, alternately washs for several times, in 60 DEG C of oven drying 15 h, obtain polystyrene-titanium dioxide core shell structure with deionized water and ethanol; It is carried out in chamber type electric resistance furnace specific segmented program intensification calcining, the carbon doping hollow titanium dioxide microballoon prepared.
Embodiment three
Prepare the hollow titanium dioxide microballoon that shell thickness is about the carbon doping of 29 nm: in 100 mL there-necked flasks, add PS template and 40 mL ethanol that 4 g removed deionized water, magnetic agitation is even, control the temperature of reaction system at 0 DEG C, by 20 mL prepared, the positive four butyl ester ethanolic solutions of metatitanic acid of 0.15 g/mL are slowly added drop-wise to reaction system, after sedimentation 24h, after slowly dripping the mixed liquor of 3mL deionized water and 6 mL ethanol, carry out hydrolysis 25h; Reaction terminates, and is undertaken centrifugal by sample, alternately washs for several times, in 60 DEG C of oven drying 15 h, obtain polystyrene-titanium dioxide core shell structure with deionized water and ethanol; It is carried out in chamber type electric resistance furnace specific segmented program intensification calcining, the carbon doping hollow titanium dioxide microballoon prepared.
Embodiment four
Prepare the hollow titanium dioxide microballoon that shell thickness is about the carbon doping of 41 nm: in 100 mL there-necked flasks, add PS template and 40 mL ethanol that 4 g removed deionized water, magnetic agitation is even, control the temperature of reaction system at 0 DEG C, by 20 mL prepared, the positive four butyl ester ethanolic solutions of metatitanic acid of 0.2 g/mL are slowly added drop-wise to reaction system, after sedimentation 24h, after slowly dripping the mixed liquor of 3mL deionized water and 6 mL ethanol, carry out hydrolysis 23h; Reaction terminates, and is undertaken centrifugal by sample, alternately washs for several times, in 60 DEG C of oven drying 15 h, obtain polystyrene-titanium dioxide core shell structure with deionized water and ethanol; It is carried out in chamber type electric resistance furnace specific segmented program intensification calcining, the carbon doping hollow titanium dioxide microballoon prepared.
Embodiment five
Prepare the hollow titanium dioxide microballoon that shell thickness is about the carbon doping of 20 nm: in 100 mL there-necked flasks, add PS template and 40 mL ethanol that 4 g removed deionized water, magnetic agitation is even, control the temperature of reaction system at 0 DEG C, by 20 mL prepared, the positive four butyl ester ethanolic solutions of metatitanic acid of 0.25 g/mL are slowly added drop-wise to reaction system, after sedimentation 24h, after slowly dripping the mixed liquor of 3mL deionized water and 6 mL ethanol, carry out hydrolysis 25h; Reaction terminates, and is undertaken centrifugal by sample, alternately washs for several times, in 60 DEG C of oven drying 15 h, obtain polystyrene-titanium dioxide core shell structure with deionized water and ethanol; It is carried out in chamber type electric resistance furnace specific segmented program intensification calcining, the carbon doping hollow titanium dioxide microballoon prepared.
Claims (10)
1. the preparation method of an in-situ carbon doping hollow titanium dioxide visible light catalyst, it is characterized in that: the cation polystyrene particle (PS) adopting monodispersity is template, take ethanol as solution system, with butyl titanate (TBT) for titanium precursors, deionized water is catalyst; The temperature controlling reaction system with ice-water bath is 0 DEG C, the ethanolic solution of butyl titanate is slowly added drop-wise in reaction system, after sedimentation a period of time, hydrolysis is carried out after dripping the mixed liquor of appropriate deionized water and ethanol, reaction terminates, sample is carried out centrifugal, washing, dry, again calcining remove cation polystyrene template, original position prepares the hollow titanium dioxide visible light catalyst of carbon doping.
2. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, it is characterized in that: in the preparation process of cation polystyrene template, cation benzyl vinyl trimethyl ammonium chloride (VTC) monomer added and the mass ratio of styrene monomer are 10%-40%.
3. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, is characterized in that: the TBT used needs to dissolve with ethanol in advance, and then slowly drips; The ethanol solution concentration of positive four butyl esters of metatitanic acid that described reaction adopts is at 0.025 ~ 0.2 g/mL, and concentration range can be used for the shell thickness of TIO2, and concentration is larger, and shell thickness is thicker.
4. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, it is characterized in that: before deionized water catalyst adds, TBT must be allowed to have the sufficient sedimentation time in cation template, is 24h; Its objective is and make TBT can carry out uniform sedimentation at template surface, add at water and fashionablely can realize " original position " at template surface and be hydrolyzed self assembly, if the sedimentation time is too short, TBT is uneven in template surface sedimentation, and TBT hydrolysis rate is exceedingly fast, finally cause the dispersiveness of the hollow titanium dioxide prepared too poor.
5. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, it is characterized in that: the catalyst deionized water as hydrolysis TBT is no more than 5% of total solvent volume, must under stirring and add with the form of mixtures of water and ethanol, wherein deionized water and ethanol volume ratio 1:2; As directly added water, local can be caused to be hydrolyzed excessive velocities, to cause the reunion that microballoon is a large amount of.
6. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, is characterized in that: to the PS/TiO of preparation
2the method for calcinating of nucleocapsid structure is that segmented program heats up: 25 DEG C are warming up to 250 DEG C, and used time 250 min, keeps 60 min; 250 DEG C are warming up to 300 DEG C, and used time 100 min, keeps 30 min; 300 DEG C are warming up to 350 DEG C, and used time 200 min, keeps 120 min; 350 DEG C are warming up to 400 DEG C, and used time 200 min, keeps 60 min; 400 DEG C are warming up to 450 DEG C, and used time 200 min, keeps 120 min; In order to ensure TiO
2before being transformed into anatase crystal completely, template can not be removed completely, and it is best that effect calcined by fire door under buttoned-up status, to ensure TiO
2carbon in crystal phase transition process exists.
7. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, it is characterized in that: described photochemical catalyst is the titania-doped microballoon of in-situ carbon, good dispersion, pattern rule, particle size is mainly distributed in 450 ~ 550 nm; There is very strong visible ray absorption, within 30 minutes, completely rhodamine B can be resolved into intermediate, water and carbon dioxide.
8. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, is characterized in that: the ethanol solution concentration of the PS template adopted is at 0.025 ~ 0.125 g/mL.
9. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, is characterized in that: the sedimentation time of described reaction is 24 h; Hydrolysis time is 20 ~ 25 h; The washing methods of described product is for alternately cleaning with deionized water and absolute ethyl alcohol; The baking temperature of described reaction is 60 DEG C, and drying time is 10 ~ 15 h.
10. the preparation method of a kind of in-situ carbon doping hollow titanium dioxide visible light catalyst as claimed in claim 1, is characterized in that: the mass ratio of the cation polystyrene particle of described butyl titanate and monodispersity is: 2-5:4.
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