CN103194731A - Method for preparing nitrogen-doped titanium dioxide porous membrane - Google Patents
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- CN103194731A CN103194731A CN2013101271665A CN201310127166A CN103194731A CN 103194731 A CN103194731 A CN 103194731A CN 2013101271665 A CN2013101271665 A CN 2013101271665A CN 201310127166 A CN201310127166 A CN 201310127166A CN 103194731 A CN103194731 A CN 103194731A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract
The invention discloses a method for preparing nitrogen-doped titanium dioxide porous membrane. The method comprises the following steps of: placing the base material in a reaction chamber of anatomic layer deposition device to deposit a TiO2 protection membrane, obtaining a titaniferous organic-inorganic composite membrane with different thickness on the surface of the base material, treating the composite membrane for 1-2 hours at 350-800 DEG C in air, oxygen or inert atmosphere, removing the organic constituents in the titaniferous organic-inorganic composite membrane, and obtaining a composite material with the nitrogen-doped titanium dioxide porous membrane deposited on the surface of the base material. The nitrogen-doped titanium dioxide porous membrane prepared by the invention has the advantages of visible-light catalytic activity and high specific surface area.
Description
Technical field
The present invention relates to the technology of preparing of titanium dioxide porous membrane, more specifically, the present invention relates to form by molecular layer deposition (MLD) method of nitrating titanium dioxide porous membrane.
Background technology
Titanium dioxide (TiO
2) photocatalytic activity is strong, cheap, advantages of environment protection because having for film, have broad application prospects in fields such as solar cell, organism photocatalytic degradation, sensing, automatically cleaning materials.Prepare TiO at present
2The method of film mainly contains methods such as liquid deposition, sol-gel, magnetron sputtering, chemical vapour deposition and ald.Wherein, ald (ALD) be by the pulse of gas phase presoma is alternately fed reactor and on the deposition matrix chemisorption and reaction form a kind of method (technology) of deposited film.ALD has film growth thickness in accurate controlled, the advantage such as step coverage is splendid, good reproducibility, film and base material bonding force are strong of atomic level, be particularly suitable for the growth of ultrathin film, in the preparation of nanotechnology and semiconducter device, have various application.Use technique for atomic layer deposition growth oxidation titanium film, more research has been arranged, but prepared film right and wrong hole film all, specific surface area is little, has a strong impact on its photocatalytic activity, and because TiO
2Greater band gap (Detitanium-ore-type TiO
2Be 3.2 eV), only UV-light is had response, thereby limited TiO
2The application of photocatalyst material.
Summary of the invention
Prepare TiO in order to overcome existing ALD technology
2The film above shortcomings the object of the present invention is to provide a kind of method of utilizing molecular layer deposition (MLD) technology to prepare the nitrating titanium dioxide porous membrane with visible light catalysis activity and high-specific surface area.
In order to obtain the deposited film of porous, can introduce organic molecule in deposition process, deposition obtains the organic and inorganic composite membrane earlier, and this deposition technique also is molecular layer deposition (MLD).Organic constituent in the above-mentioned organic-inorganic film is removed the mineral membrane that can obtain porous.
MLD is a kind of advanced person's thin film technique, film that can conformal on the substrate material surface uniform deposition, technology is simple, controllable thickness, and can carry out functionalization to mould material by the organic molecule of selecting to contain specific function group, compare with traditional method and have outstanding advantage.
The technical solution adopted in the present invention is:
(1) base material is put into the reaction chamber of atomic layer deposition apparatus, used inert nitrogen gas to purge 5-10 min, deposit then;
The MLD deposition parameter of setting is:
Temperature of reaction 80-400 oC;
Reaction source: adopt TiCl
4Or Ti (OCH (CH
3)
2)
4Be the titanium source, thanomin and malonyl chloride are organic precursor, Ti (OCH (CH
3)
2)
4The source temperature is 60
oC, thanomin source temperature is 80
OC, TiCl
4With malonyl chloride source Wen Douwei room temperature;
Carrier gas: the high pure nitrogen of 10-100 sccm;
Pulse, feel suffocated and purge time: at first with TiCl
4Or Ti (OCH (CH
3)
2)
4The sediment chamber is sent in the steam pulse, and the burst length is 0.01-0.5 s, and BHT is 5-10 s, and purge time is 10-120 s; Then the sediment chamber is sent in the pulse of thanomin steam, the burst length is 0.1-1 s, and BHT is 5-10 s, and purge time is 60-150 s; Then the sediment chamber is sent in the pulse of malonyl chloride steam, the burst length is 0.1-1 s, and BHT is 5-10 s, and purge time is 60-150 s; Again the sediment chamber is sent in the pulse of thanomin steam at last, burst length is 0.1-1 s, and BHT is 5-10 s, and purge time is 60-150 s, this namely finishes the primary depositing circulation, repeats this deposition cycle namely obtains different thickness at substrate material surface titaniferous organic and inorganic composite membrane;
(2) surface deposition that step (1) is obtained the base material of titaniferous organic and inorganic composite membrane at air, in oxygen or the inert atmosphere at 350-800
oC pyroprocessing 1-2 h removes organic constituent in the titaniferous organic and inorganic composite membrane, obtains depositing at substrate material surface the matrix material of nitrating titanium dioxide porous membrane.
The matrix material that the present invention can also obtain above-mentioned steps (2) is handled (peel off, roasting, pickling and alkali cleaning etc.), removes base material, can obtain the TiO 2 porous material of nitrating.
Aforesaid base material is the material that there are hydroxyl or defective bit in surfaces such as silicon chip, multiaperture pellumina, cupric oxide nano line, carbon nanometer spiral.
Compared with prior art, the invention has the advantages that: the molecular layer deposition method of the nitrating titanium dioxide porous membrane that a kind of preparation has visible light activity is provided, in mould material, has introduced the organic molecule of nitrogen-containing functional group, discharged NH through pyrolytic decomposition
3With TiO
2Reaction can realize in-situ doped preparation nitrating titanium dioxide, and organic constituent can obtain porous-film as template after removing simultaneously.Prepared nitrating titanium dioxide porous membrane has the excellent visible light catalytic activity, has important application value in fields such as solar cell, organism photocatalytic degradation, sensing, automatically cleaning materials.
Description of drawings
Fig. 1 is MLD deposition process synoptic diagram of the present invention.As shown in the figure, in described MLD deposition process, the titanium source is (with TiCl
4For example describes, A) at first be adsorbed on substrate material surface and with the reaction of its surface hydroxyl, at surface formation-TiCl
xSpecies (x is 2 or 3), unreacted TiCl
4Molecule pump venting; Then-TiCl
xWith the hydroxyl preferential reaction in the thanomin of sending into through pulse (B), at surface introducing-OCH
2CH
2NH
2Functional group, unnecessary thanomin molecule pump venting; Next the surface-OCH
2CH
2NH
2With the malonyl chloride of sending into through pulse (C) reaction, and at surface formation acid chloride groups, unnecessary malonyl chloride pump venting; At last, the acid chloride groups on surface and the amino preferential reaction in the thanomin (B) that pulse is sent into, finish the primary depositing circulation, and introduce hydroxyl again on the surface, for circulation next time provides reaction site, repeat the certain number of times of this deposition cycle, namely obtain the titaniferous organic-inorganic film of different thickness.
Fig. 2 A and 2B are respectively low power and the high power transmission electron microscope picture (TEM) that embodiment 2 makes sample.
Fig. 3 A is that embodiment 3 schemes at the TEM of the titaniferous organic and inorganic composite membrane sample of CuO nanowire surface deposition, and Fig. 3 B is that above-mentioned sample is at H
2: Ar is in the atmosphere of 5:95 600
oC handles 2 h and removes the TEM figure that obtains sample behind the Cu with HCl.
Fig. 4 schemes for the TEM that embodiment 4 makes sample, and illustration is high power TEM figure.
Fig. 5 A makes the x-ray photoelectron spectroscopy figure of sample for 200 circulations of deposition (cycles) among the embodiment 5, and Fig. 5 B is corresponding N 1s high resolution spectrogram.
Fig. 6 is the visible light catalysis activity evaluation result of six samples among the embodiment 1-5.
Embodiment
Embodiment 1
With the silicon chip ultrasonic 5min in ethanol that buys, dry up with nitrogen then and it is transferred to sediment chamber's (temperature is 80oC) of atomic layer deposition apparatus, use inert nitrogen gas to purge 5 min, then with TiCl
4The sediment chamber is sent in the steam pulse, and the burst length is 0.01 s, and BHT is 5 s, and purge time is 10 s; Then the sediment chamber is sent in the pulse of thanomin steam, the burst length is 0.1 s, and BHT is 5 s, and purge time is 60 s; Then the sediment chamber is sent in the pulse of malonyl chloride steam, the burst length is 0.1 s, and BHT is 5 s, and purge time is 60 s; Again the sediment chamber is sent in the pulse of thanomin steam at last, the burst length is 0.1 s, and BHT is 5 s, and purge time is 60 s, and this namely finishes the primary depositing circulation.Repeat above-mentioned deposition cycle 50 times, obtain having deposited at silicon chip the sample of titaniferous organic and inorganic composite membrane.With described sample in oxygen 350
oC roasting 2h obtains depositing at silicon chip surface the matrix material of faint yellow nitrating titanium dioxide porous membrane, and faint yellow nitrating titanium dioxide porous membrane is scraped, and namely obtains the TiO 2 porous material of nitrating, and after tested, its specific surface area is 168 m
2/ g.Photochemical catalysis test result (as Fig. 6) shows that the TiO 2 porous bill of material of this nitrating reveals visible light catalysis activity preferably, irradiation 2.5 h under visible light, methylene blue dye degraded 78.3%.
Embodiment 2
(aperture 100 nm Whatman) place sediment chamber's (temperature is 300 oC) of atomic layer deposition apparatus, use inert nitrogen gas to purge 8 min, then with Ti (OCH (CH for film diameter 25 mm, thickness 60 μ m with the multiaperture pellumina bought
3)
2)
4The sediment chamber is sent in the steam pulse, and the burst length is 0.1 s, and BHT is 8 s, and purge time is 60s; Then the sediment chamber is sent in the pulse of thanomin steam, the burst length is 0.5 s, and BHT is 8 s, and purge time is 120 s; Then the sediment chamber is sent in the pulse of malonyl chloride steam, the burst length is 0.5 s, and BHT is 8 s, and purge time is 120 s; Again the sediment chamber is sent in the pulse of thanomin steam at last, the burst length is 0.5 s, and BHT is 8 s, and purge time is 120 s, and this namely finishes the primary depositing circulation.Repeat above-mentioned deposition cycle 50 times, obtain the sample that the pellumina hole surface has deposited titaniferous organic and inorganic composite membrane.With the gained sample in air 600
OCRoasting 1h, and remove alumina formwork with 6M NaOH solution, namely obtain the TiO 2 porous nanotube of nitrating (Fig. 2 A), from electromicroscopic photograph (Fig. 2 B) as can be seen, described nitrating titanium dioxide thickness of pipe is 10 nm, its specific surface area is 192 m after tested
2/ g.Photochemical catalysis test result (as Fig. 6) shows that the TiO 2 porous nanotube of this nitrating shows the excellent visible light catalytic activity, irradiation 2.5 h under visible light, methylene blue dye degraded 100%.
Embodiment 3
With the copper mesh bought (50 orders, diameter 3.05 mm, Plano, Germany) in retort furnace with 12
oThe temperature rise rate of C/min rises to 475
OCAnd keep, obtain surface oxidation and become diameter 30-150 nm, the copper mesh of the CuO nano wire of long 10 μ m.Copper mesh behind the above-mentioned surface oxidation is transferred to sediment chamber's (temperature is 100 oC) of atomic layer deposition apparatus, uses inert nitrogen gas to purge 5 min, then with TiCl
4The sediment chamber is sent in the steam pulse, and the burst length is 0.2 s, and BHT is 5 s, and purge time is 45 s; Then the sediment chamber is sent in the pulse of thanomin steam, the burst length is 0.3 s, and BHT is 5 s, and purge time is 60 s; Then the sediment chamber is sent in the pulse of malonyl chloride steam, the burst length is 0.3 s, and BHT is 5 s, and purge time is 60 s; Again the sediment chamber is sent in the pulse of thanomin steam at last, the burst length is 0.3 s, and BHT is 5 s, and purge time is 60 s, and this namely finishes the primary depositing circulation.Repeat above-mentioned deposition cycle 50 times, obtain the sample that the CuO nanowire surface has deposited titaniferous organic and inorganic composite membrane.Can find out (Fig. 3 A) from electromicroscopic photograph, the CuO nanowire surface has deposited the titaniferous organic and inorganic composite membrane of 30 nm.The gained sample was at H after deposition was finished
2: Ar is in the atmosphere of 5:95 600
oC handles 2 h, and removes substrate Cu template (by obtaining after the reduction of CuO nano wire) with 1M HCl solution, namely obtains the TiO 2 porous nanotube of nitrating, shown in Fig. 3 B.Its specific surface area is 196 m after tested
2/ g.Photochemical catalysis test result (as Fig. 6) shows that the TiO 2 porous nanotube of this nitrating shows the excellent visible light catalytic activity, irradiation 2.5 h under visible light, methylene blue dye degraded 100%.
Embodiment 4
The cupric tartrate presoma in the 250oC pyrolysis, is obtained the copper nano-particle of about 50 nm, feed acetylene gas, at the 250oC catalyzing acetylene, synthetic spiral nano-fibre.With spiral nano-fibre thermal treatment 1 hour in the 900oC rare gas element, obtain having carbon nanometer spiral even spirane structure, about diameter 100nm.Carbon nanometer spiral is distributed on the quartz plate, is transferred to sediment chamber's (temperature is 100 oC) of atomic layer deposition apparatus after the drying, use inert nitrogen gas to purge 10 min, then with TiCl
4The sediment chamber is sent in the steam pulse, and the burst length is 0.5 s, and BHT is 10 s, and purge time is 120 s; Then the sediment chamber is sent in the pulse of thanomin steam, the burst length is 1 s, and BHT is 10 s, and purge time is 150 s; Then the sediment chamber is sent in the pulse of malonyl chloride steam, the burst length is 1 s, and BHT is 10 s, and purge time is 150 s; Again the sediment chamber is sent in the pulse of thanomin steam at last, the burst length is 1 s, and BHT is 10 s, and purge time is 150 s, and this namely finishes the primary depositing circulation.Repeat above-mentioned deposition cycle 100 times, obtain coating in carbon nanometer helical surface the sample of titaniferous organic and inorganic composite membrane.The gained sample was at H after deposition was finished
2: Ar is in the atmosphere of 5:95 600
oC handles 2 h, obtains coating in carbon nanometer helical surface the sample of nitrating titanium dioxide porous membrane, and as shown in Figure 4, illustration is the high power transmission electron microscope photo of nitrating titanium dioxide porous membrane among Fig. 4, can find out obviously that it is vesicular structure.The specific surface area of above-mentioned sample is 176 m after tested
2/ g.Photochemical catalysis test result (as Fig. 6) shows that this sample shows the excellent visible light catalytic activity, irradiation 2.5 h under visible light, methylene blue dye degraded 95.8%.
Embodiment 5
Preparation process is with embodiment 4, and cycle index is respectively 200 and 300 times, obtains two samples that carbon nanometer helical surface coats different thickness titaniferous organic and inorganic composite membrane, with these two samples respectively at H
2: Ar is in the atmosphere of 5:95 600
oC handles 2 h, obtains the carbon nanometer spiral mixture that corresponding nitrating titanium dioxide porous membrane coats.The carbon nanometer spiral mixture that the nitrating titanium dioxide porous membrane that wherein deposits 200 circulation gained is coated carries out the x-ray photoelectron spectroscopy analysis, and the result shows that nitrogen successfully mixes in the titanium oxide, as shown in Figure 5.After tested, the specific surface area of two samples is respectively 186 m
2/ g and 180m
2/ g.Two samples catalysis methylene blue activity under radiation of visible light the results are shown in shown in Figure 6.As can be seen from the figure, two samples have all shown the excellent visible light catalytic activity, irradiation 2.5 h under visible light, and methylene blue dye degrades 100% and 98.8% respectively.
The catalyst activity evaluation method:
It is 2.5 x 10 that 10 mg samples are joined 30 mL methylene blue concentration
-5In the solution of mol/L, elder generation's lucifuge stirs 1 h makes methylene blue reach adsorption equilibrium, solution is transferred under the 300W xenon lamp then, with the light of spectral filter elimination wavelength at 420nm, vigorous stirring, get 2 mL samples at regular intervals, use residual methylene blue concentration in the uv-vis spectra analytical solution behind the high speed centrifugation.
Claims (5)
1. a method for preparing the nitrating titanium dioxide porous membrane is characterized in that comprising the steps:
(1) base material is put into the reaction chamber of atomic layer deposition apparatus, used inert nitrogen gas to purge 5-10 min, deposit then;
The MLD deposition parameter of setting is:
Temperature of reaction 80-400 oC;
Reaction source: adopt TiCl
4Or Ti (OCH (CH
3)
2)
4Be the titanium source, thanomin and malonyl chloride are organic precursor, Ti (OCH (CH
3)
2)
4The source temperature is 60
oC, thanomin source temperature is 80
oC, TiCl
4With malonyl chloride source Wen Douwei room temperature;
Carrier gas: the high pure nitrogen of 10-100 sccm;
Pulse, feel suffocated and purge time: at first with TiCl
4Or Ti (OCH (CH
3)
2)
4The sediment chamber is sent in the steam pulse, and the burst length is 0.01-0.5 s, and BHT is 5-10 s, and purge time is 10-120 s; Then the sediment chamber is sent in the pulse of thanomin steam, the burst length is 0.1-1 s, and BHT is 5-10 s, and purge time is 60-150 s; Then the sediment chamber is sent in the pulse of malonyl chloride steam, the burst length is 0.1-1 s, and BHT is 5-10 s, and purge time is 60-150 s; Again the sediment chamber is sent in the pulse of thanomin steam at last, burst length is 0.1-1 s, and BHT is 5-10 s, and purge time is 60-150 s, this namely finishes the primary depositing circulation, repeats this deposition cycle namely obtains different thickness at substrate material surface titaniferous organic and inorganic composite membrane;
(2) surface deposition that step (1) is obtained the base material of titaniferous organic and inorganic composite membrane at air, in oxygen or the inert atmosphere at 350-800
oC pyroprocessing 1-2 h removes organic constituent in the titaniferous organic and inorganic composite membrane, obtains depositing at substrate material surface the matrix material of nitrating titanium dioxide porous membrane.
2. a kind of method for preparing the nitrating titanium dioxide porous membrane as claimed in claim 1 is characterized in that the matrix material that step (2) obtains is handled, and removes base material, obtains the TiO 2 porous material of nitrating.
3. a kind of method for preparing the nitrating titanium dioxide porous membrane as claimed in claim 2, it is characterized in that matrix material handle adopt peel off, roasting, pickling or alkali cleaning.
4. a kind of method for preparing the nitrating titanium dioxide porous membrane as claimed in claim 1 is characterized in that described base material is the material that there are hydroxyl or defective bit in the surface.
5. a kind of method for preparing the nitrating titanium dioxide porous membrane as claimed in claim 4 is characterized in that it is silicon chip, multiaperture pellumina, cupric oxide nano line or carbon nanometer spiral that there is the material of hydroxyl or defective bit on described surface.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498132A (en) * | 2013-09-13 | 2014-01-08 | 大连理工大学 | Method for preparing TiO2 film by gas-phase uniform deposition on basis of hydrolysis reaction |
| CN103638915A (en) * | 2013-12-16 | 2014-03-19 | 复旦大学 | High-catalytic-property TiO2 nano powder/porous material as well as preparation method and application of high-catalytic-property TiO2 nano powder/porous material |
| CN104175663A (en) * | 2014-05-29 | 2014-12-03 | 中国乐凯集团有限公司 | Ultraviolet radiation-proof transparent high-barrier thin film and applications thereof |
| CN105280389A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for dye-sensitized solar cell |
| CN105280827A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for perovskite type solar battery |
| CN105344342A (en) * | 2015-11-09 | 2016-02-24 | 复旦大学 | Photocatalyst environment purifying material based on active carbon and preparation method therefor |
| CN107295794A (en) * | 2015-02-25 | 2017-10-24 | 代尔夫特科技大学 | Control release from the particle encapsulated by molecular-layer deposition |
| CN110512189A (en) * | 2019-06-14 | 2019-11-29 | 邱越 | A kind of aperture adjustable porous metal oxide preparation method based on molecular-layer deposition |
| CN110820123A (en) * | 2019-11-15 | 2020-02-21 | 大连理工大学 | Porous color carbon fiber material and preparation method thereof |
| CN112126927A (en) * | 2019-06-24 | 2020-12-25 | 北京师范大学 | Preparation method of hydrogen storage material |
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| CN103498132A (en) * | 2013-09-13 | 2014-01-08 | 大连理工大学 | Method for preparing TiO2 film by gas-phase uniform deposition on basis of hydrolysis reaction |
| CN103638915A (en) * | 2013-12-16 | 2014-03-19 | 复旦大学 | High-catalytic-property TiO2 nano powder/porous material as well as preparation method and application of high-catalytic-property TiO2 nano powder/porous material |
| CN104175663B (en) * | 2014-05-29 | 2016-09-14 | 中国乐凯集团有限公司 | A kind of ultraviolet radiation preventing transparency high separation thin film and application thereof |
| CN104175663A (en) * | 2014-05-29 | 2014-12-03 | 中国乐凯集团有限公司 | Ultraviolet radiation-proof transparent high-barrier thin film and applications thereof |
| CN107295794A (en) * | 2015-02-25 | 2017-10-24 | 代尔夫特科技大学 | Control release from the particle encapsulated by molecular-layer deposition |
| CN105280389A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for dye-sensitized solar cell |
| CN105280827A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for perovskite type solar battery |
| CN105280827B (en) * | 2015-10-16 | 2018-08-14 | 湖北大学 | The preparation method of Ca-Ti ore type solar cell |
| CN105344342A (en) * | 2015-11-09 | 2016-02-24 | 复旦大学 | Photocatalyst environment purifying material based on active carbon and preparation method therefor |
| CN110512189A (en) * | 2019-06-14 | 2019-11-29 | 邱越 | A kind of aperture adjustable porous metal oxide preparation method based on molecular-layer deposition |
| CN112126927A (en) * | 2019-06-24 | 2020-12-25 | 北京师范大学 | Preparation method of hydrogen storage material |
| CN112126927B (en) * | 2019-06-24 | 2022-03-01 | 北京师范大学 | Preparation method of hydrogen storage material |
| CN110820123A (en) * | 2019-11-15 | 2020-02-21 | 大连理工大学 | Porous color carbon fiber material and preparation method thereof |
| CN110820123B (en) * | 2019-11-15 | 2021-06-01 | 大连理工大学 | Porous color carbon fiber material and preparation method thereof |
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