CN103556144B - A kind of nonmetal doping, titanium dioxide porous film preparation method that hole is orderly - Google Patents
A kind of nonmetal doping, titanium dioxide porous film preparation method that hole is orderly Download PDFInfo
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Abstract
That the present invention relates to a kind of nonmetal doping, that hole is orderly titanium dioxide porous film preparation method, comprises the steps: resolve into gaseous substance NH completely
3and (or) CO, CO
2reagent and titania nanoparticles or TiO 2 sol be dispersed in water or ethanol, obtained dispersion system; By prepared dispersion system through methods such as spin coating, lift, blade coating or compressing tablets, make titanium dioxide platelets, and dry at a certain temperature; Dried titanium dioxide platelets is carried out in certain vacuum degree the thermal treatment controlling temperature rise rate, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.The present invention passes through vacuum tightness, temperature rise rate during amount, the thermal treatment controlling reagent, realizes the order of the hole to titanium dioxide porous film, effective control in aperture and the Effective Doping of non-metallic element (N, C) simultaneously.
Description
Technical field
That the present invention relates to a kind of titanium dioxide porous film preparation method, particularly a kind of nonmetal doping, that hole is orderly titanium dioxide porous film preparation method.
Background technology
Capture ability and better photo-generated carrier generation owing to having better luminous energy, be separated and transmission capacity, the orderly titanium dioxide porous film material of hole can be widely used in the fields such as solar cell, sun power photodissociation hydrogen manufacturing, sensor and photocatalysis degradation organic contaminant.Research shows, the hole degree of order of titanium dioxide porous film material is higher, and it is better that its sunlight is captured performance and photo-generated carrier transfer and transmitted performance.But, due to the band gap of titanium dioxide wider (titanium dioxide has two kinds of crystal formations: rutile and anatase octahedrite, and the former band gap is 3.0eV, and the latter is 3.2eV), only can UV-light be utilized.Therefore, by negatively charged ion or cation doping, dye sensitization, means reduce its band gap with narrow-band semiconductor is combined etc., are the necessary ways expanding its light absorption.
At present, the titanium dioxide porous film material that hole is orderly is by anonizing or template synthesis.Anonizing can obtain the controlled titanium dioxide nano-pipe array thin film of pore space structure, but due to the restriction of plant and instrument, this method can only prepare the orderly titanium dioxide porous film material of hole of small area.Template also can prepare the orderly titanium dioxide nano-pipe array thin film of hole, but prepared orderly film of Nano tube array of titanium dioxide is by the restriction of template.Therefore, actual demand prepared by big area can not be met all far away with above-mentioned two kinds of preparation methods.
Based on the deficiency of anonizing and template, people is had to achieve the preparation of large-area titanium dioxide porous membrane in various ways.But the hole in prepared titanium dioxide porous film is all unordered, this feature will cause scattering behavior stronger in current carrier transmittance process, the performance of serious its performance of restriction.And up to now, various method was not all considered to regulate and control the order of hole.
In addition, orderly for the hole prepared titanium dioxide porous film material is normally reacted by realization further to the nonmetal doping modification of the orderly titanium dioxide porous film material of hole.Such step-by-step processing, not only causes the increase of preparation cost, also can cause the degradation of high-sequential titanium dioxide porous film material.Therefore, need develop an orderly titanium dioxide porous film technology of preparing of hole and realize nonmetal doping simultaneously in preparation process, can be good at afterwards solving the problem.
At present in disclosed patent documentation, Chinese patent ZL201010203358.6 discloses a kind of preparation method with the carbon and nitrogen modified nano-titanium dioxide thin film of visible light activity, and the step of this preparation method is: the etch cleaner of (1) metallic titanium surface; (2) superoxol oxidizing metallic titanium surface is adopted to form pertitanic acid nano flower-like film; (3) hydrothermal method is adopted to form titanium dioxide nano-film; (4) in ureaclastic atmosphere, roasting forms modifying titanium dioxide nano wire film.The method is by realizing carbon and nitrogen modified to titanium deoxid film to the gas making urea decomposite in heat-processed.But this method does not consider the problem forming hole in film, do not consider to regulate and control the order of hole.
Chinese patent ZL200710074630.3 discloses a kind of titanium deoxid film and preparation method thereof, this technology is that after titanium dioxide, dispersion agent, pore-forming material, part water and nitric acid being mixed, slowly grinding is opened, again remaining water is slowly added, after grinding 40--60 minute again, add emulsifying agent and continue grinding, obtain titania slurry; By scraper method masking on conductive glass, dry 12--48 hour under room temperature; Dried film is put in muffle furnace and sinters, obtained titanium deoxid film.The deficiency of the method is: (1) does not consider doping vario-property; (2) the hole order of the titanium deoxid film prepared is low.
Chinese patent application 200810198716.1 discloses a kind of preparation method of nano-titanium dioxide film photocatalyst, this method is that the ethanolic soln mix and blend of the acetum of tetrabutyl titanate and non-ionic type template is made titanium colloidal sol, through Best-Effort request, drying, high-temperature calcination, namely obtain nano-titanium dioxide film photocatalyst.The deficiency of the method is: (1) does not consider doping vario-property; (2) do not consider the structure of hole, even if the titanium deoxid film prepared is porous, its hole order is also very low.
Chinese patent ZL200910260875.4 discloses a kind of titanium deoxid film with macroporous structure and preparation method thereof, the method comprises the following steps: (1) add in the titanium dioxide of 5--10 % by weight 0.15-10.5 % by weight large pore-forming agent, the dispersion agent of 1--2 % by weight, the solvent of 15--40 % by weight and 50--75 % by weight pore-forming material, obtain the mixture of 100 % by weight, by described mixture grinding 1--2 hour, obtain titania slurry; (2) described titania slurry is coated on conductive glass by spread coating, and at 120--130 DEG C of dry 5--10 minute; (3) the described conductive glass being coated with titania slurry is sintered 0.5--2 hour at 400--500 DEG C.Another Chinese patent ZL201010116694.7 discloses a kind of method for the preparation of used by dye sensitization solar battery titanium deoxid film, described method comprises the following steps: that the titanium dioxide particle diameter of 1--10 % by weight is 5-10nm by (1), the titania powder of concentration to be the TiO 2 sol of 10-100mg/ml and the particle diameter of 5--15 % by weight be 20-40nm evenly grinds, add the pore-forming material of 80--90 % by weight, the mixture of obtain 100 % by weight is ground 0.5--2 hour; (2) described titania slurry is coated on conductive glass, and at 100--130 DEG C of dry 5--15 minute; (3) the described conductive glass being coated with titania slurry is sintered 0.5--2 hour at 450--500 DEG C.But these two kinds of methods do not consider nonmetallic ion-doped problem, do not consider the order of hole yet.
Chinese patent ZL02119304.5 discloses a kind of preparation method with high disinfecting photoactivity mesoporous titanium dioxide film, the method adopts complexing colloidal sol--gel method, in order to form mesoporous titanium dioxide film, pore-forming agent (or template) is added in colloidal sol preparation process, pore-forming agent used is a kind of amphipathic triblock copolymer macromolecular compound, by adjusting molecular-weight average and the add-on of this multipolymer, adjust film internal orifice dimension size and distribution.But the method does not consider the doping vario-property problem to porous membrane yet, do not consider to regulate and control the order of porous membrane Hole yet.
Chinese patent ZL200810053516.7 discloses a kind of preparation method of macroporous-mesoporous nanocrystalline titania film, and the method step is: (1) prepares mesoporous precursor sol; (2) synthetic polystyrene microballoon emulsion and assembling polystyrene microsphere glue crystal template; (3) dipping-pulling method prepares foramen magnum-mesoporous structure nano crystal titanium dioxide film.The invention provides a kind of by sol-gel process, adopt the high-specific surface area of the double-pore structure of prepared by block polymer and the brilliant array double-template of polystyrene (PS) glue, ordered big hole and mesoporous combination, structurally ordered, even, light transmission is good and hole wall is the TiO of the nanocrystalline structure of Anatase
2film.The method obtains the orderly thin film of titanium oxide of porous hole by template, but the method does not consider the modification problem of titanium deoxid film.
Summary of the invention
The technical problem to be solved in the present invention is: provide the titanium dioxide porous film preparation method that a kind of nonmetal doping, hole are orderly, the method synchronously can carry out the doping vario-property of non-metallic element and the regulation and control of hole order to titanium dioxide porous film, can big area prepare hole orderly, the titanium dioxide porous film of nonmetal doping modification.
The technical scheme solved the problems of the technologies described above is: the titanium dioxide porous film preparation method that a kind of nonmetal doping, hole are orderly, comprises the steps:
(1) choose that a certain amount of to decompose completely in heat treatment process and obtain gaseous substance be NH
3, CO, CO
2in a kind of, the reagent of two or three;
(2) nano level titanium dioxide powder is scattered in solvent obtains titanium oxide dispersion, after ultrasonic 5 ~ 20 minutes are carried out to titanium oxide dispersion, grind 20 ~ 120 minutes, prepare the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 50 % by weight; Or TiO 2 sol is scattered in solvent, prepares the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 50 % by weight; Or be that the TiO 2 sol of 40-90mg/ml is directly as titanium dioxide dispersion system using concentration;
(3) by the reagent described in step (1) by the concentration that this agent dissolves is made in solvent be maybe 10 ~ 80 % by weight reagent solution and step (2) in titanium dioxide dispersion system mix, the mass ratio making the reagent and titanium dioxide that can be decomposed into gaseous substance in heat treatment process is 2% ~ 20%, adopt the mode of spin coating, lift, blade coating or compressing tablet, make titanium dioxide platelets, and at temperature is 20 DEG C ~ 60 DEG C dry 0.5 ~ 4h;
(4) by dried titanium dioxide platelets in step (3) Absolute truth reciprocal of duty cycle be 0.01KPa ~ 50KPa, temperature rise rate is 0.1 DEG C/condition of min ~ 10 DEG C/min under be heated to 90 DEG C ~ 450 DEG C, and keep after being incubated 0.2 ~ 2h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.
Can decompose completely in heat treatment process and obtaining gaseous substance described in step (1) is NH
3, CO, CO
2in a kind of, two or three reagent be one in ammonium carbamate, ammonium oxalate, ammonium binoxalate, volatile salt, bicarbonate of ammonia, urea, two or more.
Step (2) and the solvent described in (3) are water or ethanol, and the solvent phase that step (2) and (3) use is same.
Further technical scheme of the present invention is: the titanium dioxide porous film preparation method that a kind of nonmetal doping, hole are orderly, comprises the steps:
(1) to decompose completely in heat treatment process and obtain gaseous substance be NH by a certain amount of
3, CO, CO
2in a kind of, the reagent of two or three;
(2) nano level titanium dioxide powder is scattered in solvent obtains titanium oxide dispersion, after ultrasonic 10 ~ 20 minutes are carried out to titanium oxide dispersion, grind 60 ~ 120 minutes, prepare the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 40 % by weight; Or TiO 2 sol is scattered in solvent, prepares the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 40 % by weight; Or be that the TiO 2 sol of 70-90mg/ml is as titanium dioxide dispersion system using concentration;
(3) by the reagent described in step (1) by the concentration that this agent dissolves is made in solvent be maybe 20 ~ 50 % by weight reagent solution and step (2) in titanium dioxide dispersion system mix, the mass ratio making the reagent and titanium dioxide that can be decomposed into gaseous substance in heat treatment process is 2% ~ 20%, adopt the mode of spin coating, lift, blade coating or compressing tablet, make titanium dioxide platelets, and at temperature is 20 DEG C ~ 60 DEG C dry 1 ~ 2h;
(4) by dried titanium dioxide platelets in step (3) Absolute truth reciprocal of duty cycle be 0.1KPa ~ 30KPa, temperature rise rate is 1 DEG C/condition of min ~ 5 DEG C/min under be heated to 100 DEG C ~ 300 DEG C, and keep after being incubated 1 ~ 2h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.
Described a kind of nonmetal doping, titanium dioxide porous film that hole is orderly is film doped with non-metallic element N and/or C.
In step (2), TiO 2 sol is scattered in solvent, after then carrying out ultrasonic 10 ~ 20 minutes, grinds 60 ~ 120 minutes, prepare the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 40 % by weight.
Described ultrasonic ultrasonic frequency is 50 ~ 60kHz, and power is 80 ~ 200W.
Owing to adopting technique scheme, a kind of nonmetal doping of the present invention, titanium dioxide porous film preparation method that hole is orderly compared with existing titanium dioxide porous film preparation method, there is following beneficial effect:
1. preparation method of the present invention will be for can resolve into gaseous substance NH completely
3and (or) CO, CO
2reagent and titania nanoparticles or TiO 2 sol Homogeneous phase mixing; then certain thickness titanium dioxide platelets is made in the mode of spin coating, lift, blade coating or compressing tablet; after drying titanium dioxide platelets is heat-treated under certain vacuum tightness and is prepared from, can big area prepare hole orderly, the titanium dioxide porous film of nonmetal doping modification.Instant invention overcomes anonizing and template can not big area prepare hole orderly titanium dioxide porous film material defect, also overcome the randomness of hole and the defect of traditional nonmetal doping modification proceed step by step when additive method prepares porous titanium dioxide thin-film.
2. the invention provides a kind of technology controlled the hole order, hole size, pattern etc. of porous titanium dioxide thin-film, the reagent that the present invention adopts for can decompose completely and to obtain gaseous substance NH in heat treatment process
3and (or) CO, CO
2reagent, in heat treatment process, limit vacuum tightness and the temperature rise rate of heat treatment container, by control add the amount of reagent, the vacuum tightness of heat treatment process and temperature rise rate, make gas NH
3and (or) CO, CO
2can if having time slowly from titanium dioxide platelets surface out, thus can control effectively to aperture, hole order under the effect of draught head.Hole radius size through this titanium dioxide porous film of experimental measurement is 10nm ~ 10 μm, and the surface energy of observing film finds out the order of hole.
3. because the decomposition of reagent makes to be filled with NH in heat treatment container
3and (or) CO, CO
2, thus realize the doping vario-property of the non-metallic element (as N, C etc.) of titanium dioxide porous film.Present invention achieves the Effective Doping modification of order to the hole of titanium dioxide porous film and non-metallic element (N, C), and to the order of the doping vario-property of non-metallic element and hole for synchronously carrying out, that prepare a kind of nonmetal doping, that hole is orderly titanium dioxide porous film, present invention reduces nonmetal doping, the preparation cost of the orderly titanium deoxid film of hole, and due to nonmetal doping, improve the spectrum respective performances of titanium dioxide porous film.
4. a kind of nonmetal doping of preparing of the present invention, titanium dioxide porous film that hole is orderly, can be used in the association areas such as solar cell, solar photolysis water hydrogen gas, sensor, organic pollutant photocatalytic degradation.Preparation method of the present invention is simple, is convenient to promote the use of, and the present invention thus preparation method also may be used for the preparation of the orderly porous membrane of the hole of other materials.
Embodiment
Embodiment one: get 5g urea and be dissolved in ethanol, obtains the urea soln that concentration is 40 % by weight; Getting particle diameter is that the titania nanoparticles 40g of 20nm is scattered in ethanol and obtains titanium oxide dispersion, (ultrasonic frequency 50kHz after ultrasonic 10min is carried out to titanium oxide dispersion, power 100W), grinding 60min, obtains the titanium dioxide dispersion system that titanium dioxide concentration is 33.6 % by weight; After the urea soln prepared and titanium dioxide dispersion system all being mixed, on conductive glass, obtain titanium dioxide platelets with spread coating, by titanium dioxide platelets dry 2h at temperature is 40 DEG C; By dried titanium dioxide platelets vacuum tightness be 0.133KPa, temperature rise rate is heated to 200 DEG C under being the condition of 1 DEG C/min, and keeps after being incubated 1h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.The mean pore size of this titanium dioxide porous film is 200nm.
Embodiment two: be averaged particle diameter is 10nm, concentration is 80mg/ml TiO 2 sol 100ml evenly grind after as titanium dioxide dispersion system (if the TiO 2 sol used condenses, just need grinding, otherwise grinding can not be needed); Getting ammonium oxalate 1g dissolves in above-mentioned titanium dioxide dispersion system; On conductive glass, titanium dioxide platelets is obtained in the mode of lift, by titanium dioxide platelets at temperature is 60 DEG C after dry 1h, by dried titanium dioxide platelets vacuum tightness be 0.1KPa, temperature rise rate is heated to 220 DEG C under being the condition of 1.6 DEG C/min, and keep after being incubated 1h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.The mean pore size of this titanium dioxide porous film is 500nm.
Embodiment three: get 2g bicarbonate of ammonia and 3g volatile salt is dissolved in the water, obtains the mixing solutions that concentration is 10 % by weight; Getting particle diameter is that the titania nanoparticles 40g of 21nm is scattered in water and obtains titanium oxide dispersion, (ultrasonic frequency 60kHz after ultrasonic 10min is carried out to titanium oxide dispersion, power 80W), grinding 90min, obtains the titanium dioxide dispersion system that titanium dioxide concentration is 40 % by weight; After the mixing solutions prepared and titanium dioxide dispersion system being mixed, on conductive glass, obtain titanium dioxide platelets with spin-coating method, by titanium dioxide platelets dry 2h at 40 DEG C; By dried titanium dioxide platelets Absolute truth reciprocal of duty cycle be 10KPa, temperature rise rate is heated to 100 DEG C under being the condition of 2 DEG C/min, and keeps after being incubated 1h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.The mean pore size of this titanium dioxide porous film is 1um.
Embodiment four: 1g urea and 1g ammonium carbamate are dissolved in the water, obtains the mixing solutions that concentration is 10 % by weight; Getting particle diameter is that the titania nanoparticles 20g of 21nm is scattered in water and obtains titanium oxide dispersion, (ultrasonic frequency 50kHz after ultrasonic 10min is carried out to titanium oxide dispersion, power 200W), grinding 120min, obtains the titanium dioxide dispersion system that titanium dioxide concentration is 40 % by weight; After the mixing solutions prepared and titanium dioxide dispersion system being mixed, on conductive glass, obtain titanium dioxide platelets with spin-coating method, by titanium dioxide platelets dry 2h at 60 DEG C; By dried titanium dioxide platelets vacuum tightness be 30KPa, temperature rise rate is heated to 200 DEG C under being the condition of 5 DEG C/min, and keeps after being incubated 2h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.The mean pore size of this titanium dioxide porous film is 1um.
Embodiment five: getting particle diameter is that the titania nanoparticles 20g of 21nm is scattered in water and obtains titanium oxide dispersion, (ultrasonic frequency 55kHz after ultrasonic 10min is carried out to titanium oxide dispersion, power 150W), grinding 120min, obtains the titanium dioxide dispersion system that titanium dioxide concentration is 40 % by weight; In dispersion system, add each 0.2g of urea, volatile salt and bicarbonate of ammonia respectively, and make it abundant dissolving; On conductive glass, titanium dioxide platelets is obtained, by titanium dioxide platelets dry 2h at 60 DEG C with spin-coating method; By dried titanium dioxide platelets vacuum tightness be 0.1KPa, temperature rise rate is heated to 300 DEG C under being the condition of 2 DEG C/min, and keeps after being incubated 2h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.The mean pore size of this titanium dioxide porous film is 200nm.
Embodiment six: be averaged the TiO 2 sol 100ml that particle diameter is 10nm, concentration is 80mg/ml and be scattered in ethanol, then (ultrasonic frequency 50kHz after ultrasonic 12min is carried out, power 100W), grind 60 minutes, obtain the titanium dioxide dispersion system that titanium dioxide concentration is 10 % by weight; Getting ammonium binoxalate 0.16g dissolves in above-mentioned titanium dioxide dispersion system; On conductive glass, titanium dioxide platelets is obtained in the mode of lift, by titanium dioxide platelets at temperature is 20 DEG C after dry 4h, by dried titanium dioxide platelets vacuum tightness be 1KPa, temperature rise rate is heated to 200 DEG C under being the condition of 2 DEG C/min, and keep after being incubated 1h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.The mean pore size of this titanium dioxide porous film is 60nm.
Replace as one of the present invention: the present invention also may be used for the preparation of the orderly porous membrane of the hole of other materials.Such as, the present invention can by changing other and can decompose completely in heat treatment process and the reagent obtaining other gaseous substances making doped with other desired non-metallic element in the titanium dioxide porous film prepared, and such as adulterate S element.
Claims (6)
1. nonmetal doping, a titanium dioxide porous film preparation method that hole is orderly, it is characterized in that: comprise the steps:
(1) choose that a certain amount of to decompose completely in heat treatment process and obtain gaseous substance be NH
3, CO, CO
2in a kind of, the reagent of two or three;
(2) nano level titanium dioxide powder is scattered in solvent obtains titanium oxide dispersion, after ultrasonic 5 ~ 20 minutes are carried out to titanium oxide dispersion, grind 20 ~ 120 minutes, prepare the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 50 % by weight; Or TiO 2 sol is scattered in solvent, prepares the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 50 % by weight; Or be that the TiO 2 sol of 40-90mg/ml is directly as titanium dioxide dispersion system using concentration;
(3) by the reagent described in step (1) by the concentration that this agent dissolves is made in solvent be maybe 10 ~ 80 % by weight reagent solution and step (2) in titanium dioxide dispersion system mix, the mass ratio making the reagent and titanium dioxide that can be decomposed into gaseous substance in heat treatment process is 2% ~ 20%, adopt the mode of spin coating, lift, blade coating or compressing tablet, make titanium dioxide platelets, and at temperature is 20 DEG C ~ 60 DEG C dry 0.5 ~ 4h;
(4) by dried titanium dioxide platelets in step (3) Absolute truth reciprocal of duty cycle be 0.01KPa ~ 50KPa, temperature rise rate is 0.1 DEG C/condition of min ~ 10 DEG C/min under be heated to 90 DEG C ~ 450 DEG C, and keep after being incubated 0.2 ~ 2h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film;
Can decompose completely in heat treatment process and obtaining gaseous substance described in step (1) is NH
3, CO, CO
2in a kind of, two or three reagent be one in ammonium carbamate, ammonium oxalate, ammonium binoxalate, volatile salt, bicarbonate of ammonia, urea, two or more.
2. a kind of nonmetal doping according to claim 1, titanium dioxide porous film preparation method that hole is orderly, it is characterized in that: step (2) and the solvent described in (3) are water or ethanol, the solvent phase that step (2) and (3) use with.
3. a kind of nonmetal doping according to claim 1, titanium dioxide porous film preparation method that hole is orderly, it is characterized in that: comprise the steps:
(1) to decompose completely in heat treatment process and obtain gaseous substance be NH by a certain amount of
3, CO, CO
2in a kind of, the reagent of two or three;
(2) nano level titanium dioxide powder is scattered in solvent obtains titanium oxide dispersion, after ultrasonic 10 ~ 20 minutes are carried out to titanium oxide dispersion, grind 60 ~ 120 minutes, prepare the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 40 % by weight; Or TiO 2 sol is scattered in solvent, prepares the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 40 % by weight; Or be that the TiO 2 sol of 70-90mg/ml is as titanium dioxide dispersion system using concentration;
(3) by the reagent described in step (1) by the concentration that this agent dissolves is made in solvent be maybe 20 ~ 50 % by weight reagent solution and step (2) in titanium dioxide dispersion system mix, the mass ratio making the reagent and titanium dioxide that can be decomposed into gaseous substance in heat treatment process is 2% ~ 20%, adopt the mode of spin coating, lift, blade coating or compressing tablet, make titanium dioxide platelets, and at temperature is 20 DEG C ~ 60 DEG C dry 1 ~ 2h;
(4) by dried titanium dioxide platelets in step (3) Absolute truth reciprocal of duty cycle be 0.1KPa ~ 30KPa, temperature rise rate is 1 DEG C/condition of min ~ 5 DEG C/min under be heated to 100 DEG C ~ 300 DEG C, and keep after being incubated 1 ~ 2h cooling under vacuum state, that obtain a kind of nonmetal doping, that hole is orderly titanium dioxide porous film.
4. a kind of nonmetal doping according to the arbitrary claim of claim 1-3, titanium dioxide porous film preparation method that hole is orderly, it is characterized in that: described a kind of nonmetal doping, titanium dioxide porous film that hole is orderly is film doped with non-metallic element N and/or C.
5. a kind of nonmetal doping according to claim 4, titanium dioxide porous film preparation method that hole is orderly, it is characterized in that: in step (2), TiO 2 sol is scattered in solvent, then after carrying out ultrasonic 10 ~ 20 minutes, grind 60 ~ 120 minutes, prepare the titanium dioxide dispersion system that titanium dioxide concentration is 5 ~ 40 % by weight.
6. a kind of nonmetal doping according to claim 5, titanium dioxide porous film preparation method that hole is orderly, it is characterized in that: described ultrasonic ultrasonic frequency is 50 ~ 60kHz, power is 80 ~ 200W.
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