CN102234133A - Semiconductor compound porous wall titanium dioxide hollow sphere material and preparation method thereof - Google Patents
Semiconductor compound porous wall titanium dioxide hollow sphere material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a semiconductor compound porous wall titanium dioxide hollow sphere material and provides a simple method for preparing the material. The method is characterized by adopting a crystal-water-containing salt, providing water required by hydrolysis of a titanium source by virtue of a reaction and taking the crystal-water-containing salt as a template for forming a titanium dioxide hollow sphere. The method comprises the followings steps of: firstly adding the crystal-water-containing salt into a non-water solvent, stirring for a period of time to obtain a suspension, adding the titanium source into the suspension, and stirring continuously; transferring the obtained reaction precursor liquid into a reactor, carrying out a liquid phase reaction for certain time at a certain temperature, and gradually releasing crystal water to hydrolyze the titanium source so as to obtain a precipitate, washing and drying the precipitate, thus the semiconductor compound titanium dioxide hollow sphere material is obtained. The preparation process provided by the invention is simple, has low cost, is environmentally-friendly and has greater application potentials; the semiconductor compound titanium dioxide hollow sphere material with full performances can be obtained by selecting different crystal-water-containing salts, and good performances are obtained when the material is applied to the field of photocatalysed and dye sensitized solar cells.
Description
Technical field
The present invention relates to the compound porous wall titanium dioxide hollow ball of a kind of semi-conductor material and preparation method thereof, be specifically related to a kind ofly contain the abundant semi-conductor composite titanium dioxide hollow ball material of salt prepared composition controllability of crystal water, belong to technical field of function materials by employing.
Background technology
The harm that causes along with energy dilemma and environmental pollution constantly aggravates, and people are urgent day by day to the application and the demand of renewable energy source.Sun power has huge advantage as renewable energy source, and emerging sun power utilizes approach to mainly contain following two: photocatalysis technology and solar cell.Titanium dioxide semiconductor material abundant as a kind of reserves and environmental protection all has good application in above two fields: since Fujishima in 1972 finds that the titanium dioxide photoelectrode surface continues to produce the phenomenon of hydrogen, conductor photocatalysis technology based on titanium dioxide has received very big concern and has obtained huge development, it can be used for degradable organic pollutant, cracking aquatic products hydrogen, aspect such as antibiotic and antifouling, is a desirable approach that solves problems such as present energy shortage and environmental pollution; Engineering institutes such as Lausanne, SUI height in 1991
Professor has reported that a kind of efficiency of conversion based on titanium dioxide nanocrystalline reaches 7.1% dye-sensitized solar cells, and the monolithic small area efficient of dye-sensitized solar cells can reach 12%, sub-modular (25cm at present
2) efficient surpassed 8%, this technical matters is simple, with low cost, is expected to break through crystalline silicon and the thin film solar cell investment is big, cost is high application bottleneck, this has also further expanded the Application Areas of titanium dioxide.
Aspect photochemical catalysis, titanium dioxide powder has good photocatalytic activity, particularly the P25 with goldschmidt chemical corporation is a series of commercialization nano TiO 2 powders of representative, shown excellent photocatalysis performance especially, yet nano TiO 2 powder reclaims difficulty, and can cause secondary pollution to former system, can't reuse under the recycle system, and the titanium dioxide of intrinsic only has ultraviolet light response, thereby limited its application at numerous areas.How simple and method preparation that cost is cheap has visible light-responded property and the titanic oxide material that is easy to reclaim has become the focus of research by technology.By the hollow ball material that titanium dioxide nanocrystalline assembles, its nanocrystalline essence has guaranteed enough big specific surface area, and micron-sized sphere sizes helps the recovery and the recycling of material simultaneously.At present, the preparation method of titanium dioxide hollow ball has been reported in existing a large amount of research, such as polystyrene spheres template, carbon ball template method, bubble template, microemulsion method etc., by mixing or compoundly also can realizing visible light-responded property.Yet adopt the method for single stage method original position synthesis nano compound titanium dioxide hollow ball to yet there are no report.
Aspect dye-sensitized solar cells, battery structure mainly comprises several parts such as porous semiconductor electrode film, dye sensitizing agent, redox electrolytes matter, counter electrode and conductive substrates.Its principle of work is: dye molecule absorbs behind the sunlight from the ground state transition to excited state, the electronics of excited state dyestuff is injected in the conduction band of Nano semiconductor, transfer to conductive substrates subsequently, be transferred to counter electrode through external loop, the dyestuff that is in oxidation state is reduced the ionogen reducing/regenerating of attitude, the ionogen of oxidation state is accepted electronics at counter electrode and is reduced, thereby has finished a working cycle of electron transport.In these processes, two of simultaneous back of the body reaction: be injected into the electronics in the semi-conductor conduction band and the complex reaction of the electron acceptor(EA) in oxidation state dyestuff or the ionogen.The how positive reaction of strengthening electronic transport process suppresses the back of the body reaction of charge recombination, is an emphasis of current dye-sensitized solar cells research work.Collection and transmission efficiency by the raising electronics are to realize the main path of high efficiency dye sensitization solar cell, collection and the transmission efficiency of existing research report by titanium dioxide being mixed can improving electronics, but tend to disadvantageous effect open circuit voltage.Therefore by the synthetic new material of new preparation method, just seem extremely important to realize the collection transmission efficiency and the open circuit voltage that improve electronics simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of compound porous wall titanium dioxide hollow ball of semi-conductor material of excellent performance, to improve the applicability of titanium dioxide hollow ball in photochemical catalysis and dye-sensitized solar cells field.
Another object of the present invention is to provide the simple of a kind of above-mentioned materials and the cost low-cost preparation method is compound to the nano level that titanium dioxide hollow ball carries out original position to realize single stage method.
Describe the present invention below in detail.
The present invention adopts a kind of simple method, utilizes the salt contain crystal water, the template that hydrolysis required water in titanium source is provided and forms by reaction as titanium dioxide hollow ball, thus obtain controllable component, semi-conductor composite titanium dioxide hollow ball material that performance is abundant.This titanium dioxide hollow ball can be applicable to photochemical catalysis and dye-sensitized solar cells field, has all shown good performance.
A) contain the preparation of the salt suspension liquid of crystal water
The salt that contains crystal water comprise Zinc Sulphate Heptahydrate, iron vitriol, heptahydrate, seven water single nickel salts, magnesium sulfate heptahydrate, cupric sulfate pentahydrate, six water chromium sulphates, Cadmium Sulphate, manganous sulfate be representative contain crystal water vitriol; Four water zinc phosphates, phosphate dihydrate iron, Copper phosphate (Cu3(PO4)2) trihydrate, three water secondary magnesium phosphates, six water Plessy's greens be representative contain crystal water phosphoric acid salt; And the mixture of above-mentioned two or more salt.Solvent adopts non-aqueous solvent, comprise with methyl alcohol, ethanol, propyl alcohol, butanols, Virahol being the liquid alcohols of representative, hexane, heptane, octane, decane, hexanaphthene, octane-iso are the liquid alkanes of representative, and they two or more press the mixed solvent of arbitrary proportion.The crystal water salt that contains of difference amount is joined in the above-mentioned solvent, obtain suspension liquid after stirring for some time under the room temperature, the concentration range of salt in solvent that contains crystal water is at 0.01～1M.
B) preparation of reaction precursor liquid
Add a certain amount of titanium source in the suspension liquid that contains crystal water salt of step a) preparation, the mixture of tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, iso-butyl titanate, titanium tetrachloride, titanous chloride and their two or more arbitrary proportions is adopted in the titanium source.Under agitation slowly drip above-mentioned titanium source, continue to stir, the molar ratio range that wherein contains crystal water salt and titanium source is 1: 0.1～5.
C) preparation of semi-conductor composite titanium dioxide hollow ball
The precursor liquid of step b) gained is moved in the reaction vessel, obtained the target precipitation in 0.5～120 hour at 60～350 ℃ of temperature range internal reactions, the throw out washing is drying to obtain semi-conductor composite titanium dioxide hollow ball material.
Semi-conductor composite titanium dioxide hollow ball preparation method's disclosed by the invention advantage is:
Preparation method disclosed by the invention has adopted the salt that contains crystal water to come the synthesis of titanium dioxide hollow ball material first, contains crystal water salt and have triple role in system: the crystal water that slowly discharges in the heat-processed provides titanium source hydrolysis reaction required water; The class spheric salt that forms is as the template of titanium dioxide hollow ball formation in advance; Be the source material that semi-conductor composite titanium dioxide hollow ball semi-conductor generates simultaneously.The semi-conductor composite titanium dioxide hollow ball that obtains is used for photochemical catalysis and the equal tool of dye-sensitized solar cells has shown good performance.
The present invention has adopted simple and the cheap preparation technology of cost, and the range of choice of reaction system raw material is wide, utilizes the modification of the compound realization titanic oxide material of original position.By the titanium dioxide hollow ball material that can enrich, can realize the visible light-responded property of titanium dioxide, to strengthen utilization ratio to sunlight to the selection available that contains crystal water salt; Simultaneously, the compound electron transport ability that improves titanium dioxide, thereby the effciency of energy transfer of lifting dye-sensitized solar cells.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of zinc oxide composite titanium dioxide hollow ball, shows that the material that obtains is pure anatase phase titanium dioxide.
Fig. 2 is the stereoscan photograph of zinc oxide composite titanium dioxide hollow ball, shows that the material that obtains has micron-sized hollow ball structure.
Fig. 3 is the transmission electron microscope photo of zinc oxide composite titanium dioxide hollow ball, shows that the micron order hollow ball wall that obtains is assembled by little crystal grain, and has nano pore structure.
Fig. 4 is the high-resolution-ration transmission electric-lens photo of zinc oxide composite titanium dioxide hollow ball, and the titanium dioxide nanocrystalline of the ball wall that shows the micron order hollow ball that obtains about by 8 nanometers assembles.
Fig. 5 is the ultraviolet degradation tropeolin-D rate curve of zinc oxide composite titanium dioxide hollow ball, shows that the semi-conductor composite titanium dioxide hollow ball that obtains has excellent photocatalysis performance.
Fig. 6 is the UV, visible light diffuse-reflectance absorption spectrum of different semi-conductor composite titanium dioxide hollow balls, curve 1 is a ferric oxide compound titanium dioxide hollow ball among the figure, curve 2 is a cobalt oxide compound titanium dioxide hollow ball, curve 3 is a magnesium oxide compound titanium dioxide hollow ball, shows that the semi-conductor composite titanium dioxide hollow ball that obtains has high visible light response.
Embodiment
Introduce embodiments of the invention below, to understanding of the present invention, but the present invention is limited to embodiment absolutely not with further increase.
Embodiment 1:
Get the 0.5g Zinc Sulphate Heptahydrate and join in the 50ml alcohol solvent, obtain white suspension liquid after stirring 2h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain white precipitate at 240 ℃ of solvent thermal reaction 24h, throw out promptly gets zinc oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Test through XRD, the product that obtains is anatase structured (as shown in Figure 1), its microcosmic scanning electron microscope (SEM) photo as shown in Figure 2, transmission electron microscope photo has shown that the ball wall of hollow ball is assembled by titanium dioxide nanocrystalline, and having pore passage structure (as shown in Figure 3, Figure 4), energy spectrum analysis has proved the existence of zinc oxide.
The zinc oxide composite titanium dioxide hollow ball material that obtains is used for ultraviolet degradation tropeolin-D (MO) experiment, used light source is the 500W high voltage mercury lamp, the concentration of tropeolin-D is 10mg/L, through UV-irradiation 6min, the methyl orange degradation rate is more than 90%, and degradation efficiency is better than Degussa P25 nano TiO 2 powder (as shown in Figure 5).In addition, the zinc oxide composite titanium dioxide hollow ball that obtains is used for the assembling of dye-sensitized solar cells, test result shows, compound titanium dioxide hollow ball more not, the open circuit voltage of battery and short-circuit current all have tangible lifting, efficiency of conversion can reach 3.56%, has promoted 24% than the efficiency of conversion of not titania-doped hollow ball battery.
Embodiment 2:
Get the 1g iron vitriol and join in the 50ml methanol solvate, obtain brown suspension liquid after stirring 1h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain yellow mercury oxide at 180 ℃ of solvent thermal reaction 48h, throw out promptly gets ferric oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Test through XRD, the product that obtains is anatase structured, transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of ferric oxide, and UV, visible light diffuse-reflectance absorption spectrum has shown that product has high visible light response (as shown in Figure 6).
The ferric oxide composite titanium dioxide hollow ball that obtains is used for visible light degraded tropeolin-D (MO) experiment, and used light source is the 500W xenon lamp, and the concentration of tropeolin-D is 10mg/L, and test result shows that product has good visible light photocatalysis active.
Embodiment 3:
Get the 0.5g heptahydrate and join in the 50ml propyl alcohol solvent, obtain brown suspension liquid after stirring 1h, dropping 2ml isopropyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain the khaki color precipitation at 240 ℃ of solvent thermal reaction 12h, throw out promptly gets cobalt oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Test through XRD, the product that obtains is anatase structured, transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of cobalt oxide, and UV, visible light diffuse-reflectance absorption spectrum has shown that product has high visible light response (as shown in Figure 6).
The cobalt oxide composite titanium dioxide hollow ball material that obtains is used for visible light degraded tropeolin-D (MO) experiment, and used light source is the 500W xenon lamp, and the concentration of tropeolin-D is 10mg/L, and test result shows that product has good visible light photocatalysis active.
Embodiment 4:
Get the 0.3g magnesium sulfate heptahydrate and join in the 50ml isopropanol solvent, obtain white suspension liquid after stirring 1h, dropping 1ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain faint yellow precipitation at 240 ℃ of solvent thermal reaction 48h, throw out promptly gets magnesium oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Test through XRD, the product that obtains is anatase structured, transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved magnesian existence, and UV, visible light diffuse-reflectance absorption spectrum has shown that product has high visible light response (as shown in Figure 6).
The magnesium oxide composite titanium dioxide hollow ball material that obtains is used for visible light degraded tropeolin-D (MO) experiment, and used light source is the 500W xenon lamp, and the concentration of tropeolin-D is 10mg/L, and test result shows that product has good visible light photocatalysis active.
Embodiment 5:
Get 2g six water chromium sulphates and join in the 50ml propyl carbinol solvent, obtain the deep green suspension liquid after stirring 1h, dropping 1ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reflux, react 120h down at 300 ℃ and obtain the deep green precipitation, throw out promptly gets chromic oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Test through XRD, the product that obtains is anatase structured, transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of chromic oxide, and UV, visible light diffuse-reflectance absorption spectrum has shown that product has high visible light response.
The chromic oxide composite titanium dioxide hollow ball material that obtains is used for visible light degraded tropeolin-D (MO) experiment, and used light source is the 500W xenon lamp, and the concentration of tropeolin-D is 10mg/L, and test result shows that product has good visible light photocatalysis active.
Embodiment 6:
Get the 0.1g Zinc Sulphate Heptahydrate and join in the 50ml alcohol solvent, obtain white suspension liquid after stirring 0.5h, dropping 0.5ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain white precipitate at 180 ℃ of solvent thermal reaction 1h, throw out promptly gets zinc oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Through the XRD test, the product that obtains is anatase structured, and transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of zinc oxide.
Embodiment 7:
Get the 10g Zinc Sulphate Heptahydrate and join in the 50ml normal hexane solvent, obtain white suspension liquid after stirring 4h, dropping 1ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain white precipitate at 80 ℃ of solvent thermal reaction 48h, throw out promptly gets zinc oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Through the XRD test, the product that obtains is anatase structured, and transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of zinc oxide.
Embodiment 8:
Get the 5g Zinc Sulphate Heptahydrate and join in the 50ml alcohol solvent, obtain white suspension liquid after stirring 4h, dropping 1ml titanium tetrachloride in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reflux, react 96h down at 120 ℃ and obtain white precipitate, throw out promptly gets zinc oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.
Embodiment 9:
Get the 1g Zinc Sulphate Heptahydrate and join in the 50ml octane-iso solvent, obtain white suspension liquid after stirring 4h, dropping 1ml titanium tetrachloride in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain white precipitate at 180 ℃ of solvent thermal reaction 48h, throw out promptly gets zinc oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.
Embodiment 10:
Get the 1g iron vitriol and join in the 25ml tetradecane solvent, obtain brown suspension liquid after stirring 4h, dropping 2ml isopropyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reflux, react 48h down at 300 ℃ and obtain yellow mercury oxide, throw out promptly gets ferric oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Through the XRD test, the product that obtains is anatase structured.
Embodiment 11:
Get 2g four water zinc phosphates and join in the 50ml alcohol solvent, obtain white suspension liquid after stirring 2h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reflux, react 24h down at 180 ℃ and obtain white precipitate, throw out with the acetate washing, is used ethanol and deionized water wash earlier again, promptly gets zinc oxide composite titanium dioxide hollow ball material after the drying.Through the XRD test, the product that obtains is anatase structured.
Embodiment 12:
Get 2g phosphate dihydrate iron and join in the 50ml octane solvent, obtain brown suspension liquid after stirring 2h, dropping 2ml isopropyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reflux, react 12h down at 240 ℃ and obtain yellow mercury oxide, throw out is used the salt acid elution earlier, uses ethanol and deionized water wash again, promptly gets ferric oxide composite titanium dioxide hollow ball material after the drying.Through the XRD test, the product that obtains is anatase structured.
Embodiment 13:
Get 0.5g Zinc Sulphate Heptahydrate and 0.5g iron vitriol and join in the 50ml alcohol solvent, obtain pale brown look suspension liquid after stirring 4h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain yellow mercury oxide at 240 ℃ of solvent thermal reaction 24h, throw out promptly gets zinc oxide and ferric oxide binary compound titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Through the XRD test, the product that obtains is anatase structured, and transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of zinc oxide and ferric oxide.
Embodiment 14:
Get 0.9g Zinc Sulphate Heptahydrate and 0.1g iron vitriol and join in the 50ml alcohol solvent, obtain light yellow suspension liquid after stirring 4h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain light-yellow precipitate at 240 ℃ of solvent thermal reaction 24h, throw out promptly gets zinc oxide and ferric oxide binary compound titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Through the XRD test, the product that obtains is anatase structured, and transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of zinc oxide and ferric oxide.
Embodiment 15:
Get 0.3g Zinc Sulphate Heptahydrate, 0.3g iron vitriol and 0.3g heptahydrate and join in the 50ml alcohol solvent, obtain pale brown look suspension liquid after stirring 2h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain yellow mercury oxide at 240 ℃ of solvent thermal reaction 24h, throw out promptly gets zinc oxide, ferric oxide and cobalt oxide ternary compound titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Through the XRD test, the product that obtains is anatase structured, and transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of zinc oxide and ferric oxide.
Embodiment 16:
Get in the mixed solvent that the 0.5g Zinc Sulphate Heptahydrate joins 25ml ethanol and 25ml octane, obtain white suspension liquid after stirring 4h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain white precipitate at 240 ℃ of solvent thermal reaction 24h, throw out promptly gets zinc oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Survey 0 examination through XRD, the product that obtains is anatase structured, and transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of zinc oxide.
Embodiment 17:
Get in the mixed solvent that the 0.5g Zinc Sulphate Heptahydrate joins 45ml ethanol and 5ml octane, obtain white suspension liquid after stirring 4h, dropping 2ml tetrabutyl titanate in the suspension liquid, continue to stir reaction precursor liquid.The precursor liquid that obtains is moved in the reactor, obtain white precipitate at 240 ℃ of solvent thermal reaction 24h, throw out promptly gets zinc oxide composite titanium dioxide hollow ball material with ethanol and deionized water wash after the drying.Through the XRD test, the product that obtains is anatase structured, and transmission electron microscope photo has shown that hollow ball is assembled by titanium dioxide nanocrystalline, and energy spectrum analysis has proved the existence of zinc oxide.
Claims (10)
1. the compound porous wall titanium dioxide hollow ball of semi-conductor material is characterized in that:
(1) hollow ball of micron-scale is interconnected by nano-crystalline granule and assembles, and forms the wall of nano-porous structure;
(2) semiconductor composite and titanium dioxide nanocrystalline realize that at Nano grade original position is compound;
(3) semiconductor composite comprises zinc oxide, ferric oxide, cobalt oxide, nickel oxide, cupric oxide, chromic oxide, aluminum oxide, Cadmium oxide or manganese oxide.
2. by the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 1 preparation methods, it is characterized in that the salt that will contain crystal water joins in the non-aqueous solvent, obtain suspension liquid after the stirring,, continue to stir toward wherein adding the titanium source; To carry out liquid phase reaction in the reaction precursor liquid immigration reactor that obtain, crystal water discharges gradually and makes the hydrolysis of titanium source obtain precipitation, and the throw out washing is dry.
3. according to the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 2 preparation methods,, it is characterized in that the salt of crystal water is selected from a kind of in crystal water vitriol and/or the crystal water phosphoric acid salt, two or more mixture.
4. according to the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 2 preparation methods,, it is characterized in that crystal water vitriol comprises Zinc Sulphate Heptahydrate, iron vitriol, heptahydrate, seven water single nickel salts, magnesium sulfate heptahydrate, cupric sulfate pentahydrate, six water chromium sulphates, Cadmium Sulphate, manganous sulfate; Crystal water phosphoric acid salt comprises four water zinc phosphates, phosphate dihydrate iron, Copper phosphate (Cu3(PO4)2) trihydrate, three water secondary magnesium phosphates, six water Plessy's greens.
5. according to the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 2 preparation methods, it is characterized in that comprising with methyl alcohol, ethanol, propyl alcohol, butanols, Virahol to be the liquid alcohols of representative, with hexane, heptane, octane, decane, hexanaphthene, octane-iso be the liquid alkanes of representative, and they two or more press the mixed solvent of arbitrary proportion.
6. according to the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 2 preparation methods, the concentration range of salt in non-aqueous solvent that contains crystal water is at 0.01～1M, and churning time is greater than 10min.
7. according to the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 2 preparation methods, the titanium source is characterized in that adopting the mixture of tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, iso-butyl titanate, titanium tetrachloride, titanous chloride and their two or more arbitrary proportions.
8. according to the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 2 preparation methods, the molar ratio range that contains the salt of crystal water and titanium source is 1: 0.1～5.
9. according to the compound porous wall titanium dioxide hollow ball of the described semi-conductor of claim 2 preparation methods, it is characterized in that adopting solvent thermal and heating reflux reaction, range of reaction temperature exists
60℃～
350℃, reaction time range exists
0.
5～
120Hour.
10. according to claim
1The compound porous wall titanium dioxide hollow ball of described semi-conductor material is characterized in that being applicable to photochemical catalysis and dye-sensitized solar cells field.
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