CN103556144A - Preparation method of non-metal-doped titanium dioxide porous film with ordered pores - Google Patents
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Abstract
The invention relates to a preparation method of a non-metal-doped titanium dioxide porous film with ordered pores. The preparation method comprises the following steps of: uniformly dispersing a reagent which is completely decomposed into gaseous substances NH3 and(or) CO and CO2 and titanium dioxide nano-particles or titanium dioxide soil into water or alcohol to prepare a dispersion system; preparing titanium dioxide slices by the prepared dispersion system through methods such as spin-coating, lifting, scraping or tabletting, and drying under a certain temperature; and thermally treating the dried titanium dioxide slices in a certain vacuum degree to control heat-up velocity to prepare the non-metal-doped titanium dioxide porous film with ordered pores. According to the preparation method disclosed by the invention, effective control of order and pore diameter of pores of the titanium dioxide porous film as well as effective doping of non-metal materials (N and C) is realized at the same time by controlling the amount of the reagent, the vacuum degree and the heat-up velocity during thermal treatment.
Description
Technical field
The present invention relates to titanium dioxide porous film preparation method a kind of titanium dioxide porous film preparation method, particularly a kind of nonmetal doping, that hole is orderly.
Background technology
Owing to having better luminous energy, capture ability and better photo-generated carrier generation, separation 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 its sunlight captures that performance and photo-generated carrier shift and to transmit performance better.Yet, due to the band gap of titanium dioxide wider (titanium dioxide has two kinds of crystal formations: rutile and anatase octahedrite, the former band gap is 3.0 eV, the latter is 3.2 eV), only can utilize UV-light.Therefore, by negatively charged ion or cation doping, dye sensitization, the means such as be combined with narrow-band semiconductor, reducing its band gap, is the necessary ways of expanding its light absorption.
At present, the orderly titanium dioxide porous film material of hole is by anonizing or template synthesis.Anonizing can obtain the controlled titanium dioxide nano-pipe array thin film of pore space structure, and still, due to the restriction of plant and instrument, this method can only be prepared the orderly titanium dioxide porous film material of hole of small area.Template also can be prepared the orderly titanium dioxide nano-pipe array thin film of hole, but prepared orderly film of Nano tube array of titanium dioxide is subject to the restriction of template.Therefore, with above-mentioned two kinds of preparation methods, all can not meet actual demand prepared by big area far away.
Deficiency based on anonizing and template, has people with the whole bag of tricks, to realize the preparation of large-area titanium dioxide porous membrane.Yet the hole in prepared titanium dioxide porous film is all unordered, this feature, by causing scattering behavior stronger in current carrier transmittance process, seriously restricts the performance of its performance.And up to now, the whole bag of tricks did not all consider the order of hole to regulate and control.
In addition, the nonmetal doping modification of the orderly titanium dioxide porous film material of hole is normally further reacted the orderly titanium dioxide porous film material of the hole preparing to realization.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 to develop an orderly titanium dioxide porous film technology of preparing of hole and in preparation process, realize nonmetal doping simultaneously, can be good at afterwards addressing the above problem.
In current 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 this preparation method's step is: the etching on (1) metal titanium surface is cleaned; (2) adopt superoxol oxidizing metallic titanium using surface to form pertitanic acid nano flower-like film; (3) adopt hydrothermal method to form titanium dioxide nano-film; (4) in ureaclastic atmosphere, roasting forms modifying titanium dioxide nano wire film.The method is by making gas that urea decomposites in heat-processed realize carbon and nitrogen modified to titanium deoxid film.But this method does not consider to form in film the problem of hole, do not consider the order of hole to regulate and control.
Chinese patent ZL200710074630.3 discloses a kind of titanium deoxid film and preparation method thereof, this technology is slowly to grind and open after titanium dioxide, dispersion agent, pore-forming material, part water and nitric acid are mixed, again remaining water is slowly added, grind again after 40--60 minute, add emulsifying agent and continue to grind, obtain titania slurry; By scraper method masking, on conductive glass, under room temperature, be dried 12--48 hour; Dried film is put in muffle furnace and carries out sintering, make 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 preparing 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 to titanium colloidal sol, through dipping lift, be dried, high-temperature calcination, 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 preparing 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: that (1) adds the large pore-forming agent of 0.15-10.5 % by weight, the solvent of the dispersion agent of 1--2 % by weight, 15--40 % by weight and the pore-forming material of 50--75 % by weight in the titanium dioxide of 5--10 % by weight, obtain the mixture of 100 % by weight, described mixture is ground to 1--2 hour, obtain titania slurry; (2) described titania slurry is coated on conductive glass by spread coating, and at 120--130 ℃ of dry 5--10 minute; (3) by the described conductive glass that is coated with titania slurry at 400--500 ℃ of sintering 0.5--2 hour.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 titania powder that particle diameter that (1) is 5-10nm, the concentration TiO 2 sol that is 10-100mg/ml and 5--15 % by weight by the titanium dioxide particle diameter of 1--10 % by weight is 20-40nm evenly grinds, the pore-forming material that adds 80--90 % by weight, grinds 0.5--2 hour by the mixture of 100 % by weight that obtain; (2) described titania slurry is coated on conductive glass, and at 100--130 ℃ of dry 5--15 minute; (3) by the described conductive glass that is coated with titania slurry at 450--500 ℃ of sintering 0.5--2 hour.But these two kinds of methods are not considered 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, in colloidal sol preparation process, added pore-forming agent (or template), 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 distribute.But the method is not considered the doping vario-property problem to porous membrane yet, do not consider the order of porous membrane Hole to regulate and control 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 is prepared foramen magnum-mesoporous structure nano crystal titanium dioxide film.The invention provides a kind of by sol-gel process, adopt the double-pore structure of prepared by block polymer and the brilliant array bimodulus of polystyrene (PS) glue plate, ordered big hole and mesoporous combination high-specific surface area, structurally ordered, even, light transmission is good and the TiO of the nanocrystalline structure that hole wall is Anatase
2film.The method is to obtain the orderly thin film of titanium oxide of porous hole by template, but the method is not considered the modification problem of titanium deoxid film.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of nonmetal doping, the orderly titanium dioxide porous film preparation method of hole are provided, the method can synchronously be carried 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 titanium dioxide porous film orderly, nonmetal doping modification.
The technical scheme solving the problems of the technologies described above is: a kind of nonmetal doping, the orderly titanium dioxide porous film preparation method of hole, comprise the steps:
(1) choose that a certain amount of in heat treatment process, to decompose and obtain gaseous substance be completely NH
3, CO, CO
2in a kind of, two or three reagent;
(2) nano level titanium dioxide powder is scattered in and in solvent, obtains titanium oxide dispersion, titanium oxide dispersion is carried out after ultrasonic 5～20 minutes, grind 20～120 minutes, preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～50 % by weight; Or TiO 2 sol is scattered in solvent, and preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～50 % by weight; Or the TiO 2 sol that is 40-90mg/ml using concentration as titanium dioxide dispersion is directly;
(3) concentration of the reagent described in step (1) maybe being made this agent dissolves in solvent is that reagent solution and the system of the titanium dioxide dispersion in step (2) of 10～80 % by weight mixes, make in heat treatment process, to be decomposed into the reagent of gaseous substance and the mass ratio of titanium dioxide is 2%～20 %, adopt spin coating, lift, the mode of blade coating or compressing tablet, make titanium dioxide thin slice, and be dry 0.5～4h at 20 ℃～60 ℃ in temperature;
(4) by dried titanium dioxide thin slice in step (3), in Absolute truth reciprocal of duty cycle, be that 0.01KPa～50 KPa, temperature rise rate are to be heated to 90 ℃～450 ℃ under the condition of 0.1 ℃/min～10 ℃/min, and keep cooling under vacuum state after being incubated 0.2～2h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.
Described in step (1) in heat treatment process, to decompose and obtain gaseous substance be completely NH
3, CO, CO
2in reagent a kind of, two or three be in ammonium carbamate, ammonium oxalate, ammonium binoxalate, volatile salt, bicarbonate of ammonia, urea a kind of, two or more.
Solvent described in step (2) and (3) is water or ethanol, and the solvent phase that step (2) and (3) are used is same.
Further technical scheme of the present invention is: a kind of nonmetal doping, the orderly titanium dioxide porous film preparation method of hole, comprise the steps:
(1) in heat treatment process, to decompose and obtain gaseous substance be completely NH by a certain amount of
3, CO, CO
2in a kind of, two or three reagent;
(2) nano level titanium dioxide powder is scattered in and in solvent, obtains titanium oxide dispersion, titanium oxide dispersion is carried out after ultrasonic 10～20 minutes, grind 60～120 minutes, preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～40 % by weight; Or TiO 2 sol is scattered in solvent, and preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～40 % by weight; Or the TiO 2 sol that is 70-90mg/ml using concentration as titanium dioxide dispersion is;
(3) concentration of the reagent described in step (1) maybe being made this agent dissolves in solvent is that reagent solution and the system of the titanium dioxide dispersion in step (2) of 20～50 % by weight mixes, make in heat treatment process, to be decomposed into the reagent of gaseous substance and the mass ratio of titanium dioxide is 2%～20 %, adopt spin coating, lift, the mode of blade coating or compressing tablet, make titanium dioxide thin slice, and be dry 1～2h at 20 ℃～60 ℃ in temperature;
(4) by dried titanium dioxide thin slice in step (3), in Absolute truth reciprocal of duty cycle, be that 0.1 KPa～30KPa, temperature rise rate are to be heated to 100 ℃～300 ℃ under the condition of 1 ℃/min～5 ℃/min, and keep cooling under vacuum state after being incubated 1～2h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.
Titanium dioxide porous film described a kind of nonmetal doping, that hole is orderly is the film doped with non-metallic element N and/or C.
In step (2), TiO 2 sol is scattered in solvent, then carries out, after ultrasonic 10～20 minutes, grinding 60～120 minutes, preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～40 % by weight.
Described ultrasonic ultrasonic frequency is 50～60kHz, and power is 80～200W.
Owing to adopting technique scheme, titanium dioxide porous film preparation method a kind of nonmetal doping of the present invention, that hole is orderly compares with existing titanium dioxide porous film preparation method, has following beneficial effect:
1. preparation method of the present invention will be for can resolve into gaseous substance NH completely
3(or) CO, CO
2reagent evenly mix with titania nanoparticles or TiO 2 sol; then with spin coating, lift, the mode of blade coating or compressing tablet makes certain thickness titanium dioxide thin slice; after drying titanium dioxide thin slice is heat-treated and is prepared under certain vacuum tightness, can big area prepare hole titanium dioxide porous film orderly, nonmetal doping modification.The present invention has overcome anonizing and template can not big area be prepared the defect of the orderly titanium dioxide porous film material of hole, also overcome the randomness of hole when additive method is prepared porous titanium dioxide thin-film and the defect of traditional nonmetal doping modification proceed step by step.
2. the invention provides a kind of technology that the hole order of porous titanium dioxide thin-film, hole size, pattern etc. are controlled, the reagent that the present invention adopts for can decompose and obtain gaseous substance NH completely in heat treatment process
3(or) CO, CO
2reagent, in heat treatment process, limited 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
3(or) CO, CO
2can be if having time slowly from titanium dioxide slice surfaces out under the effect of draught head, thus can control effectively to aperture, hole order.Hole radius size through this titanium dioxide porous film of experimental measurement is 10nm～10 μ m, and the order of hole can be found out in the surface of observing film.
3. because the decomposition of reagent makes to be full of in heat treatment container NH
3(or) CO, CO
2thereby, realize the doping vario-property of the non-metallic element (as N, C etc.) of titanium dioxide porous film.The present invention has realized the Effective Doping modification to the order of the hole of titanium dioxide porous film and non-metallic element (N, C), and the doping vario-property of non-metallic element is carried out for synchronizeing with the order of hole, prepare titanium dioxide porous film a kind of nonmetal doping, that hole is orderly, the present invention has reduced preparation cost nonmetal doping, the orderly titanium deoxid film of hole, and due to nonmetal doping, improved the spectrum respective performances of titanium dioxide porous film.
4. titanium dioxide porous film a kind of nonmetal doping that the present invention prepares, 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, be convenient to promote the use of, so and the present invention's preparation method also can be orderly for the hole of other materials the preparation of porous membrane.
Embodiment
Embodiment mono-: get 5g urea and be dissolved in ethanol, obtain the urea soln that concentration is 40 % by weight; The titania nanoparticles 40g that gets particle diameter and be 20nm is scattered in and in ethanol, obtains titanium oxide dispersion, titanium oxide dispersion is carried out to (ultrasonic frequency 50kHz after ultrasonic 10min, power 100W), grind 60min, obtaining titanium dioxide concentration is the titanium dioxide dispersion system of 33.6 % by weight; After the urea soln preparing and titanium dioxide dispersion system is all mixed, obtaining titanium dioxide thin slice with spread coating on conductive glass, is dry 2h at 40 ℃ by titanium dioxide thin slice in temperature; By dried titanium dioxide thin slice, in vacuum tightness, be that 0.133KPa, temperature rise rate are to be heated to 200 ℃ under the condition of 1 ℃/min, and keep cooling under vacuum state after being incubated 1h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.The mean pore size of this titanium dioxide porous film is 200nm.
Embodiment bis-: after the TiO 2 sol 100ml that to be averaged particle diameter and to be 10nm, concentration be 80mg/ml evenly grinds as titanium dioxide dispersion system (just need to grind if the TiO 2 sol using has condensed, otherwise can not need to grind); Getting ammonium oxalate 1g dissolves in above-mentioned titanium dioxide dispersion system; In the mode lifting, on conductive glass, obtain titanium dioxide thin slice, by titanium dioxide thin slice, in temperature, be at 60 ℃, to be dried after 1h, by dried titanium dioxide thin slice, in vacuum tightness, be that 0.1KPa, temperature rise rate are to be heated to 220 ℃ under the condition of 1.6 ℃/min, and keep cooling under vacuum state after being incubated 1h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.The mean pore size of this titanium dioxide porous film is 500nm.
Embodiment tri-: get 2g bicarbonate of ammonia and 3g volatile salt is dissolved in the water, obtain the mixing solutions that concentration is 10 % by weight; The titania nanoparticles 40g that gets particle diameter and be 21nm is scattered in and in water, obtains titanium oxide dispersion, titanium oxide dispersion is carried out to (ultrasonic frequency 60kHz after ultrasonic 10min, power 80W), grind 90min, obtaining titanium dioxide concentration is the titanium dioxide dispersion system of 40 % by weight; After the mixing solutions preparing and titanium dioxide dispersion system is mixed, with spin-coating method, on conductive glass, obtain titanium dioxide thin slice, by titanium dioxide thin slice dry 2h at 40 ℃; By dried titanium dioxide thin slice, in Absolute truth reciprocal of duty cycle, be that 10KPa, temperature rise rate are to be heated to 100 ℃ under the condition of 2 ℃/min, and keep cooling under vacuum state after being incubated 1h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.The mean pore size of this titanium dioxide porous film is 1um.
Embodiment tetra-: 1g urea and 1g ammonium carbamate are dissolved in the water, obtain the mixing solutions that concentration is 10 % by weight; The titania nanoparticles 20g that gets particle diameter and be 21nm is scattered in and in water, obtains titanium oxide dispersion, titanium oxide dispersion is carried out to (ultrasonic frequency 50kHz after ultrasonic 10min, power 200W), grind 120min, obtaining titanium dioxide concentration is the titanium dioxide dispersion system of 40 % by weight; After the mixing solutions preparing and titanium dioxide dispersion system is mixed, with spin-coating method, on conductive glass, obtain titanium dioxide thin slice, by titanium dioxide thin slice dry 2h at 60 ℃; By dried titanium dioxide thin slice, in vacuum tightness, be that 30KPa, temperature rise rate are to be heated to 200 ℃ under the condition of 5 ℃/min, and keep cooling under vacuum state after being incubated 2h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.The mean pore size of this titanium dioxide porous film is 1um.
Embodiment five: the titania nanoparticles 20g that gets particle diameter and be 21nm is scattered in and in water, obtains titanium oxide dispersion, titanium oxide dispersion is carried out to (ultrasonic frequency 55kHz after ultrasonic 10min, power 150W), grind 120min, obtaining titanium dioxide concentration is the titanium dioxide dispersion system of 40 % by weight; In dispersion system, add respectively each 0.2g of urea, volatile salt and bicarbonate of ammonia, and make it abundant dissolving; With spin-coating method, on conductive glass, obtain titanium dioxide thin slice, by titanium dioxide thin slice dry 2h at 60 ℃; By dried titanium dioxide thin slice, in vacuum tightness, be that 0.1KPa, temperature rise rate are to be heated to 300 ℃ under the condition of 2 ℃/min, and keep cooling under vacuum state after being incubated 2h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.The mean pore size of this titanium dioxide porous film is 200 nm.
Embodiment six: being averaged particle diameter is that the TiO 2 sol 100ml that 10nm, concentration are 80mg/ml is scattered in ethanol, then carry out (ultrasonic frequency 50kHz after ultrasonic 12min, power 100W), grind 60 minutes, obtaining titanium dioxide concentration is the titanium dioxide dispersion system of 10 % by weight; Getting ammonium binoxalate 0.16g dissolves in above-mentioned titanium dioxide dispersion system; In the mode lifting, on conductive glass, obtain titanium dioxide thin slice, by titanium dioxide thin slice, in temperature, be at 20 ℃, to be dried after 4h, by dried titanium dioxide thin slice, in vacuum tightness, be that 1KPa, temperature rise rate are to be heated to 200 ℃ under the condition of 2 ℃/min, and keep cooling under vacuum state after being incubated 1h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.The mean pore size of this titanium dioxide porous film is 60nm.
As a kind of replacement of the present invention: the preparation of the porous membrane that the present invention also can be orderly for the hole of other materials.For example, the present invention can be by changing in the titanium dioxide porous film that other reagent that can decompose and obtain other gaseous substances in heat treatment process completely make to prepare doped with the non-metallic element of other needs, and S element for example adulterates.
Claims (7)
1. titanium dioxide porous film preparation method nonmetal doping, that hole is orderly, is characterized in that: comprise the steps:
(1) choose that a certain amount of in heat treatment process, to decompose and obtain gaseous substance be completely NH
3, CO, CO
2in a kind of, two or three reagent;
(2) nano level titanium dioxide powder is scattered in and in solvent, obtains titanium oxide dispersion, titanium oxide dispersion is carried out after ultrasonic 5～20 minutes, grind 20～120 minutes, preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～50 % by weight; Or TiO 2 sol is scattered in solvent, and preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～50 % by weight; Or the TiO 2 sol that is 40-90mg/ml using concentration as titanium dioxide dispersion is directly;
(3) concentration of the reagent described in step (1) maybe being made this agent dissolves in solvent is that reagent solution and the system of the titanium dioxide dispersion in step (2) of 10～80 % by weight mixes, make in heat treatment process, to be decomposed into the reagent of gaseous substance and the mass ratio of titanium dioxide is 2%～20 %, adopt spin coating, lift, the mode of blade coating or compressing tablet, make titanium dioxide thin slice, and be dry 0.5～4h at 20 ℃～60 ℃ in temperature;
(4) by dried titanium dioxide thin slice in step (3), in Absolute truth reciprocal of duty cycle, be that 0.01KPa～50 KPa, temperature rise rate are to be heated to 90 ℃～450 ℃ under the condition of 0.1 ℃/min～10 ℃/min, and keep cooling under vacuum state after being incubated 0.2～2h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.
2. titanium dioxide porous film preparation method a kind of nonmetal doping according to claim 1, that hole is orderly, is characterized in that: described in step (1) in heat treatment process, to decompose and obtain gaseous substance be completely NH
3, CO, CO
2in reagent a kind of, two or three be in ammonium carbamate, ammonium oxalate, ammonium binoxalate, volatile salt, bicarbonate of ammonia, urea a kind of, two or more.
3. titanium dioxide porous film preparation method a kind of nonmetal doping according to claim 1, that hole is orderly, is characterized in that: the solvent described in step (2) and (3) is water or ethanol, and the solvent phase that step (2) and (3) are used is same.
4. titanium dioxide porous film preparation method a kind of nonmetal doping according to claim 1, that hole is orderly, is characterized in that: comprise the steps:
(1) in heat treatment process, to decompose and obtain gaseous substance be completely NH by a certain amount of
3, CO, CO
2in a kind of, two or three reagent;
(2) nano level titanium dioxide powder is scattered in and in solvent, obtains titanium oxide dispersion, titanium oxide dispersion is carried out after ultrasonic 10～20 minutes, grind 60～120 minutes, preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～40 % by weight; Or TiO 2 sol is scattered in solvent, and preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～40 % by weight; Or the TiO 2 sol that is 70-90mg/ml using concentration as titanium dioxide dispersion is;
(3) concentration of the reagent described in step (1) maybe being made this agent dissolves in solvent is that reagent solution and the system of the titanium dioxide dispersion in step (2) of 20～50 % by weight mixes, make in heat treatment process, to be decomposed into the reagent of gaseous substance and the mass ratio of titanium dioxide is 2%～20 %, adopt spin coating, lift, the mode of blade coating or compressing tablet, make titanium dioxide thin slice, and be dry 1～2h at 20 ℃～60 ℃ in temperature;
(4) by dried titanium dioxide thin slice in step (3), in Absolute truth reciprocal of duty cycle, be that 0.1 KPa～30KPa, temperature rise rate are to be heated to 100 ℃～300 ℃ under the condition of 1 ℃/min～5 ℃/min, and keep cooling under vacuum state after being incubated 1～2h, obtain titanium dioxide porous film a kind of nonmetal doping, that hole is orderly.
5. according to the titanium dioxide porous film preparation method a kind of nonmetal doping, that hole is orderly described in the arbitrary claim of claim 1-4, it is characterized in that: titanium dioxide porous film described a kind of nonmetal doping, that hole is orderly is the film doped with non-metallic element N and/or C.
6. titanium dioxide porous film preparation method a kind of nonmetal doping according to claim 5, that hole is orderly, it is characterized in that: in step (2), TiO 2 sol is scattered in solvent, then carry out after ultrasonic 10～20 minutes, grind 60～120 minutes, preparing titanium dioxide concentration is the titanium dioxide dispersion system of 5～40 % by weight.
7. titanium dioxide porous film preparation method a kind of nonmetal doping according to claim 6, that hole is orderly, is characterized in that: described ultrasonic ultrasonic frequency is 50～60kHz, and power is 80～200W.
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| CN109569559A (en) * | 2019-01-15 | 2019-04-05 | 宁波石墨烯创新中心有限公司 | A kind of preparation method of photochemical catalyst |
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| CN110075903B (en) * | 2019-05-30 | 2022-03-22 | 河北麦森钛白粉有限公司 | Preparation method of C, N co-doped nano titanium dioxide |
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| CN110395772B (en) * | 2019-08-06 | 2022-06-21 | 湖北卓熙氟化股份有限公司 | Preparation method of cobalt trifluoride |
| CN112213005A (en) * | 2020-10-13 | 2021-01-12 | 新余学院 | Titanium dioxide/carbon dot composite film pressure sensor and preparation method thereof |
| CN112213005B (en) * | 2020-10-13 | 2022-04-29 | 新余学院 | Titanium dioxide/carbon dot composite film pressure sensor and preparation method thereof |
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