CN101723442A - Method for preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method - Google Patents
Method for preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method Download PDFInfo
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Abstract
The invention discloses a method for preparing a nitrogen-doped titanic acid nano tube by a hydrothermal cosolvent method, which relates to a method for preparing a nitrogen-doped titanic acid nano tube. The method solves the problems of poor stability of the titanic acid nano tube obtained by the conventional hydrothermal synthetic method and poor effect of degrading organic pollutants through photocatalysis. The method comprises the following steps: firstly, putting titanium dioxide into sodium hydroxide solution and triethanolamine to perform hydrothermal reaction so as to obtain a reaction product; secondly, cleaning the reaction product, and then drying the reaction product in vacuum; and thirdly, thermally treating the reaction product in a muffle furnace to form the nitrogen-doped titanic acid nano tube. The method adopts the triethanolamine as a reaction raw material to generate the nitrogen-doped titanic acid nano tube having good thermal stability and complete tube wall and containing an H2Ti2O5H2O crystalline substance; and the catalytic rate constant shown by the nitrogen-doped titanic acid nano tube for degrading methyl orange is 0.00921, which is 9 times of the catalytic rate constant (0.00109) shown by the nano titanium dioxide for degrading the methyl orange.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen-doped titanic acid nanotube.
Background technology
Purposes and special tubular structure receive much concern titanate radical nanopipe because of it has widely.Hoyer P adopted anonizing to prepare titania nanotube on alumina formwork in 1996; Kasuga T used Hydrothermal Preparation in 1998 titanium dioxide base nano pipe so far is the focus and emphasis that research that presoma prepares nanotube becomes the research of field of nanometer material technology the inside with titanium dioxide.Be that the method that presoma prepares nanotube mainly contains electrochemical process, oxidation reduction process, atomic deposition method, the auxiliary synthesis method of template etc. with titanium dioxide, at present based on template synthesis method and hydrothermal method.
But the tube wall of the titanium nanotube that hydrothermal synthesis method obtains is thinner, can lose water of constitution in heat treatment process, and the tube wall interfloor distance dwindles, and tubular structure begins to destroy in the time of 300 ℃, and nanotube becomes and subsides, thereby can't carry out pyroprocessing.
Summary of the invention
The objective of the invention is in order to solve the titanate radical nanopipe poor stability that existing hydrothermal synthesis method obtains, and the problem of photocatalysis degradation organic contaminant weak effect, the invention provides a kind of method of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method
The method of a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method of the present invention realizes by following steps: one, be 1: 1～5 ratio by volume with sodium hydroxide and trolamine with both mix blended liquid, then with blended liquid ultra-sonic dispersion 20～40min, again anatase-type nanometer titanium dioxide is added in the blended liquid, then blended liquid is moved in the hydrothermal reactor, the sealing hydrothermal reactor, self-heating is cooled to room temperature after reacting 12～20h under 150～200 ℃ of conditions then, supernatant liquor in the elimination hydrothermal reactor gets reaction product again, wherein, the volumetric molar concentration of sodium hydroxide solution is 8～15mol/L, and the long-pending ratio of titanium dioxide quality and blend liquid is 1g: 20～50mL; Two, the reaction product that will obtain through step 1 is neutral with salt acid elution to washings, is neutral with deionized water wash to washings again, then with reaction product at 100～130 ℃ of following vacuum-drying 5～8h; Three, will the reaction product after step 2 is handled put into and be incubated 5～6h after retort furnace is warming up to 280～320 ℃ with the speed of 2～3 ℃/min, naturally cooling promptly gets the nitrogen-doped titanic acid nanotube then.
The particle diameter of anatase-type nanometer titanium dioxide is 8～30nm among the present invention.
Can also the reaction product after step 2 is handled in the step 3 of the present invention put into and be incubated 0.5～2h after retort furnace is warming up to 100～120 ℃ with the speed of 5 ℃/min, and then be incubated 2h after being warming up to 280～320 ℃ with the speed of 1 ℃/min, naturally cooling then.
Can also the reaction product after step 2 is handled in the step 3 of the present invention put into and be incubated 2～4h after retort furnace is warming up to 160～180 ℃ with the speed of 5 ℃/min, and then be incubated 4h after being warming up to 280～320 ℃ with the speed of 2 ℃/min, naturally cooling then.
The present invention adopts trolamine (a kind of excellent surfactant and pattern are moulded agent) as reaction raw materials, nitrogen element in the trolamine can directly be doped in the nanotube in reaction process, thus synthetic Heat stability is good, pattern homogeneous, the active high nitrogen-doped titanic acid nanotube of light-catalyzed reaction of obtaining.The present invention adopts hydro-thermal cosolvent method to prepare the thicker nitrogen-doped titanic acid nanotube of tube wall, and adopt low temperature rise rate to heat-treat, avoid the nitrogen-doped titanic acid nanotube in heat treatment process, to lose the drawback that water of constitution, tube wall interfloor distance dwindle, tubular structure destroys, nanotube becomes and subsides, obtained the nitrogen-doped titanic acid nanotube of good stability.
The nitrogen-doped titanic acid nanotube that method of the present invention prepares contains H
2Ti
2O
5H
2The crystalline state material of O, its pattern homogeneous, the length-to-diameter ratio height, specific surface area is big, and light-catalyzed reaction is active high, can improve the ability of absorption and degradable organic pollutant.
The specific surface area of the nitrogen-doped titanic acid nanotube that preparation method of the present invention obtains reaches 168m
2/ g above (adopting nitrogen adsorption/desorption method), specific surface area is big, is the surface-area (27.7278m of existing nano titanium oxide
2/ g) more than 6 times.In photocatalytic degradation tropeolin-D test, adopting nitrogen-doped titanic acid nanotube of the present invention is catalyzer, behind photocatalytic degradation 180min, in the reaction solution in the concentration of tropeolin-D and the reaction solution ratio of the starting point concentration of tropeolin-D (be designated as C/C
0) be 0.074515, it is complete that the tropeolin-D organic pollutant in the reaction solution is close to catalyzed degradation; And be in the reaction system of catalyzer with the nano titanium oxide, behind the photocatalytic degradation 180min, the C/C of reaction solution
0Be 0.639207, its catalyzed degradation ability.By the dynamics data analytical procedure, adopt the pseudo-first-order reaction kinetics equation to analyze, the apparent catalytic rate constant of nitrogen-doped titanic acid nanotube of the present invention degraded tropeolin-D is 0.00921, is 9 times of apparent catalytic rate constant (0.00109) of nano titanium dioxide degradable tropeolin-D.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) shape appearance figure of the nitrogen-doped titanic acid nanotube of embodiment one; Fig. 2 be embodiment one the nitrogen-doped titanic acid nanotube carry out X-ray diffraction (XRD) test pattern; Fig. 3 is X ray electronic spectrum (XPS) graphic representation of the nitrogen-doped titanic acid nanotube of embodiment one; Fig. 4 is the degradation effect graphic representation of the reaction solution under the photocatalytic degradation tropeolin-D different time of the nitrogen-doped titanic acid nanotube of embodiment 15 and nano titanium oxide, wherein
Be the degradation effect curve of existing nano titanium oxide, ● be the degradation effect curve of nitrogen-doped titanic acid nanotube.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment nitrogen-doped titanic acid nanotube realizes by following steps: one, be 1: 1～5 ratio by volume with sodium hydroxide solution and trolamine with both mix blended liquid, then with the blended liquid ultra-sonic dispersion, again anatase-type nanometer titanium dioxide is added in the blended liquid, then blended liquid is moved in the hydrothermal reactor, the sealing hydrothermal reactor, self-heating is cooled to room temperature after reacting 12～20h under 150～200 ℃ of conditions then, supernatant liquor in the elimination hydrothermal reactor gets reaction product again, wherein, the volumetric molar concentration of sodium hydroxide solution is 8～15mol/L, and the long-pending ratio of titanium dioxide quality and blend liquid is 1g: 20～50mL; Two, will through reaction product that step 1 obtains with the salt acid elution to the neutrality again with deionized water wash to neutral, then with reaction product at 100～130 ℃ of following vacuum-drying 5～8h; Three, will the reaction product after step 3 is handled put into and be incubated 5～6h after retort furnace is warming up to 280～320 ℃ with the speed of 2～3 ℃/min, naturally cooling promptly gets the nitrogen-doped titanic acid nanotube then.
Transmission electron microscope (TEM) shape appearance figure of the nitrogen Doped with Titanium nanotube that present embodiment obtains as shown in Figure 1, as seen, present embodiment has obtained the titanium nanotube, its pattern homogeneous, length-to-diameter ratio height, and tubular structure is complete, does not have collapse phenomenon.
Present embodiment is carried out X-ray diffraction (XRD) test pattern with the nitrogen Doped with Titanium nanotube that obtains, test pattern as shown in Figure 2, as seen from Figure 2, the titanate radical nanopipe of present embodiment contains H
2Ti
2O
5H
2O crystalline state material is titanate radical nanopipe.X ray electronic spectrum (XPS) graphic representation of the nitrogen-doped titanic acid nanotube of present embodiment as seen from Figure 3, has the existence of N element as shown in Figure 3 in the titanate radical nanopipe of present embodiment, the N element that successfully mixed is described, has obtained the nitrogen-doped titanic acid nanotube.
The specific surface area of the nitrogen-doped titanic acid nanotube of present embodiment mode reaches 168m
2/ g above (adopting nitrogen adsorption-desorption method), specific surface area is big; Light-catalyzed reaction is active high, can improve the ability of absorption and degradable organic pollutant.
Embodiment two: present embodiment and embodiment one are different be in the step 1 be by volume with sodium hydroxide and trolamine 1: 3 ratio with both mix blended liquid.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different with embodiment one or two is to be ultra-sonic dispersion 20～40min in the ultrasonic wave of 180～300W with blended liquid at power in the step 1.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one, two or three are different is that the particle diameter of anatase-type nanometer titanium dioxide in the step 1 is 8～30nm.Other step and parameter are identical with embodiment one, two or three.
Anatase-type nanometer titanium dioxide is the commercially available prod in the present embodiment.
Embodiment five: present embodiment and embodiment one to four are different is that the long-pending ratio of titanium dioxide quality and blend liquid is 1g: 40mL in the step 1.Other step and parameter are identical with embodiment one to four.
Embodiment six: present embodiment and embodiment one to five are different be in the step 1 after reacting 14～18h under 160～190 ℃ of conditions self-heating be cooled to room temperature.Other step and parameter are identical with embodiment one to five.
Embodiment seven: present embodiment and embodiment one to five are different be in the step 1 behind reaction 16h under 180 ℃ of conditions self-heating be cooled to room temperature.Other step and parameter are identical with embodiment one to five.
Embodiment eight: present embodiment and embodiment one to seven are different is that the reaction product volumetric molar concentration that will obtain through step 1 in the step 2 is that the salt acid elution of 0.1～0.5mol/L is to neutral.Other step and parameter are identical with embodiment one to seven.
Embodiment nine: present embodiment and embodiment one to seven are different be in the step 2 with reaction product at 120 ℃ of following vacuum-drying 6h.Other step and parameter are identical with embodiment one to seven.
Embodiment ten: present embodiment and embodiment one to nine are different is will the reaction product after step 2 is handled in the step 3 to put into to be incubated 6h after retort furnace is warming up to 300 ℃ with the speed of 2 ℃/min.Other step and parameter are identical with embodiment one to nine.
Embodiment 11: present embodiment and embodiment ten are different is can also the reaction product after step 2 is handled in the step 3 to put into to be incubated 0.5～2h after retort furnace is warming up to 100～120 ℃ with the speed of 5 ℃/min, and then be incubated 2h after being warming up to 280～320 ℃ with the speed of 1 ℃/min, naturally cooling then.Other step and parameter are identical with embodiment one to ten.
Embodiment 12: present embodiment and embodiment 11 are different is can also the reaction product after step 2 is handled in the step 3 to put into to be incubated 1h after retort furnace is warming up to 120 ℃ with the speed of 5 ℃/min, and then be incubated 2h after being warming up to 300 ℃ with the speed of 1 ℃/min, naturally cooling then.Other step and parameter are identical with embodiment 11.
Embodiment 13: present embodiment and embodiment one to ten are different is can also the reaction product after step 2 is handled in the step 3 to put into to be incubated 2～4h after retort furnace is warming up to 160～180 ℃ with the speed of 5 ℃/min, and then be incubated 4h after being warming up to 280～320 ℃ with the speed of 2 ℃/min, naturally cooling then.Other step and parameter are identical with embodiment one to ten.
Embodiment 14: present embodiment and embodiment 13 are different is can also the reaction product after step 2 is handled in the step 3 to put into to be incubated 3h after retort furnace is warming up to 180 ℃ with the speed of 5 ℃/min, and then be incubated 2h after being warming up to 300 ℃ with the speed of 2 ℃/min, naturally cooling then.Other step and parameter are identical with embodiment 13.
Embodiment 15: the preparation method of present embodiment nitrogen-doped titanic acid nanotube realizes by following steps: one, with the 10mL volumetric molar concentration be the trolamine of the sodium hydroxide solution of 10mol/L and 10mL mix blended liquid, be ultra-sonic dispersion 30min in the ultrasonic wave of 180W with blended liquid at power then, again the 0.4g anatase-type nanometer titanium dioxide is added in the blended liquid, then blended liquid is moved in the hydrothermal reaction kettle, the sealing hydrothermal reaction kettle, self-heating is cooled to room temperature behind reaction 20h under 150 ℃ of conditions then, and the supernatant liquor in the elimination hydrothermal reaction kettle gets reaction product again; Two, will be through the reaction product volumetric molar concentration that step 1 obtains the salt acid elution of 0.1mol/L to the neutrality again with deionized water wash to neutral, then with reaction product in vacuum drying oven with vacuum-drying 6h under 120 ℃ the condition; Three, will the reaction product after step 3 is handled put into and be incubated 6h after retort furnace is warming up to 300 ℃ with the speed of 2 ℃/min, naturally cooling gets the nitrogen-doped titanic acid nanotube then.
The particle diameter of the anatase-type nanometer titanium dioxide of present embodiment is 12～16nm, is provided with your chemical industry company limited by last hypo.
Present embodiment adopts nitrogen adsorption/desorption method that the titanate radical nanopipe that obtains is carried out specific area measuring, and recording specific surface area is 187.7330m
2/ g as a comparison, adopts the specific surface area means of testing of this enforcement that existing nano titanium oxide (going up hypo provides with your chemical industry company limited) has been carried out the specific surface area test, and test result is 27.7278m
2/ g is starkly lower than the nitrogen-doped titanic acid nanotube of present embodiment.
Present embodiment is carried out the experiment of photocatalytic degradation tropeolin-D to the nitrogen-doped titanic acid nanotube that obtains, experiment condition is as follows: do light source with 100W straight pipe type high voltage mercury lamp (ultraviolet predominant wavelength is 365nm), place the nitrogen-doped titanic acid nanotube of the present embodiment of methyl orange solution that the 500ml mass concentration is 40mg/L and 0.2g in the reactor, make nitrogen-doped titanic acid nanotube and methyl orange solution thorough mixing even unglazed according to filling air under the condition, open the high voltage mercury lamp light source then, timing begins the photocatalytic degradation experiment.And sampling at set intervals, get the supernatant reaction solution behind the centrifugation 30min, utilize ultraviolet-visible pectrophotometer to carry out the mensuration of reaction solution absorbancy, thereby measure the organic degradation effect of nitrogen-doped titanic acid nano pipe photochemical catalyst degraded tropeolin-D.As a comparison, present embodiment adopts identical above-mentioned photocatalytic degradation tropeolin-D experiment parameter, and the photocatalytic degradation ability of existing nano titanium oxide (going up hypo provides with your chemical industry company limited) is measured.The nitrogen-doped titanic acid nanotube of present embodiment and the photocatalytic degradation degradation performance of Methyl orange of nano titanium oxide as shown in Figure 4, among the figure
Be the degradation effect curve of nano titanium oxide, ● be the degradation effect curve of nitrogen-doped titanic acid nanotube, the ratio of the concentration of the methyl orange solution the when ordinate zou of figure is t for the photocatalytic degradation time and the starting point concentration of methyl orange solution (is designated as C/C
0).As seen from Figure 4, after the photocatalytic degradation 180min, the C/C of nitrogen-doped titanic acid nanotube
0Value is 0.074515, the C/C of nano titanium oxide
0Value is 0.639207, and the degradation effect of nitrogen-doped titanic acid nanotube is higher than the degradation effect of existing nano titanium oxide, illustrates that the ability of photocatalysis to degrade organic matter tropeolin-D of nitrogen-doped carbon nanometer pipe is strong, and photocatalysis degradation organic contaminant is effective.
Present TiO
2The dynamics research of photocatalysis to degrade organic matter generally adopts Langmuir-Hinshelwood (L-H) model to retouch, and in the dynamics data analytical procedure, usually adopts the pseudo-first-order reaction kinetics equation to analyze light-catalyzed reaction, and is as follows:
In the formula: C
0, the reactant concn when C is respectively the starting point concentration of reactant and time t, K
BBe the apparent speed constant.
According to (C/C among Fig. 4
0The apparent speed constant of the nitrogen-doped titanic acid nano pipe photochemical catalyst of linear regression vs.t) degraded methyl orange solution is 0.00921, is 9 times of apparent speed constant (0.00104) of nano titanium dioxide photocatalysis degraded methyl orange solution.
Embodiment 16: the preparation method of present embodiment nitrogen-doped titanic acid nanotube realizes by following steps: one, with the 10mL volumetric molar concentration be the trolamine of the sodium hydroxide solution of 10mol/L and 30mL mix blended liquid, be ultra-sonic dispersion 30min in the ultrasonic wave of 300W with blended liquid at power then, again the 1.2g anatase-type nanometer titanium dioxide is added in the blended liquid, then blended liquid is moved in the hydrothermal reaction kettle that tetrafluoroethylene is a substrate, the sealing hydrothermal reaction kettle, self-heating is cooled to room temperature behind reaction 12h under 180 ℃ of conditions then, and the supernatant liquor in the elimination hydrothermal reaction kettle gets reaction product again; Two, will be through the reaction product volumetric molar concentration that step 1 obtains the salt acid elution of 0.1mol/L to the neutrality again with deionized water wash to neutral, then with reaction product in vacuum drying oven with vacuum-drying 6h under 120 ℃ the condition; Three, will the reaction product after step 3 is handled put into and be incubated 0.5h after retort furnace is warming up to 120 ℃ with the speed of 5 ℃/min, and then be incubated 2h after being warming up to 300 ℃ with the speed of 1 ℃/min, naturally cooling gets the nitrogen-doped titanic acid nanotube then.
Present embodiment adopts nitrogen adsorption-desorption method that the titanate radical nanopipe that obtains is carried out specific area measuring, and recording specific surface area is 168.7440m
2/ g as a comparison, adopts the specific surface area means of testing of this enforcement that existing nano titanium oxide (going up hypo provides with your chemical industry company limited) has been carried out the specific surface area test, and test result is 27.7278m
2/ g, the specific surface area of the nitrogen-doped titanic acid nanotube of present embodiment is 6.1 times of specific surface area of existing nano titanium oxide.
The nitrogen-doped titanic acid nanotube Heat stability is good of present embodiment, tube wall is complete.
Claims (10)
1. the method for a preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method, the preparation method who it is characterized in that the nitrogen-doped titanic acid nanotube realizes by following steps: one, be 1: 1～5 ratio by volume with sodium hydroxide solution and trolamine with both mix blended liquid, then with blended liquid ultra-sonic dispersion 20～40min, again anatase-type nanometer titanium dioxide is added in the blended liquid, then blended liquid is moved in the hydrothermal reactor, the sealing hydrothermal reactor, self-heating is cooled to room temperature after reacting 12～20h under 150～200 ℃ of conditions then, supernatant liquor in the elimination hydrothermal reactor gets reaction product again, wherein, the volumetric molar concentration of sodium hydroxide solution is 8～15mol/L, and the long-pending ratio of titanium dioxide quality and blend liquid is 1g: 20～50mL; Two, will through reaction product that step 1 obtains with the salt acid elution to the neutrality again with deionized water wash to neutral, then with reaction product at 100～130 ℃ of following vacuum-drying 5～8h; Three, will the reaction product after step 3 is handled put into and be incubated 5～6h after retort furnace is warming up to 280～320 ℃ with the speed of 2～3 ℃/min, naturally cooling promptly gets the nitrogen-doped titanic acid nanotube then.
2. the method for a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method according to claim 1, it is characterized in that in the step 1 with sodium hydroxide and trolamine be by volume 1: 3 ratio with both mix blended liquid.
3. the method for a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method according to claim 1 and 2, the particle diameter that it is characterized in that anatase-type nanometer titanium dioxide in the step 1 is 8～30nm.
4. the method for a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method according to claim 3 is characterized in that in the step 1 that self-heating is cooled to room temperature after reacting 14～18h under 160～190 ℃ of conditions.
5. the method for a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method according to claim 3 is characterized in that in the step 1 that self-heating is cooled to room temperature behind reaction 16h under 180 ℃ of conditions.
6. according to the method for claim 1,2,4 or 5 described a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method, it is characterized in that the long-pending ratio of titanium dioxide quality and blend liquid is 1g: 40mL in the step 1.
7. the method for a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method according to claim 6 is characterized in that in the step 2 reaction product at 120 ℃ of following vacuum-drying 6h.
8. according to the method for claim 1,2,4,5 or 7 described a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method, it is characterized in that in the step 3 will the reaction product after step 2 is handled putting into and be incubated 6h after retort furnace is warming up to 300 ℃ with the speed of 2 ℃/min.
9. according to the method for claim 1,2,4,5 or 7 described a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method, it is characterized in that in the step 3 can also the reaction product after step 2 is handled putting into and be incubated 0.5～2h after retort furnace is warming up to 100～120 ℃ with the speed of 5 ℃/min, and then be incubated 2h after being warming up to 280～320 ℃ with the speed of 1 ℃/min, naturally cooling then.
10. according to the method for claim 1,2,4,5 or 7 described a kind of preparing nitrogen-doped titanic acid nano tube by hydrothermal cosolvent method, it is characterized in that in the step 3 can also the reaction product after step 2 is handled putting into and be incubated 2～4h after retort furnace is warming up to 160～180 ℃ with the speed of 5 ℃/min, and then be incubated 4h after being warming up to 280～320 ℃ with the speed of 2 ℃/min, naturally cooling then.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983928A (en) * | 2010-11-10 | 2011-03-09 | 河南师范大学 | Preparation method of titanate nanotube codoped with ions of nitrogen and rare earth elements |
| CN102115913A (en) * | 2011-01-22 | 2011-07-06 | 西北大学 | Preparation method of titanium dioxide nanotube film |
| CN102962089A (en) * | 2012-11-26 | 2013-03-13 | 杭州电子科技大学 | Method for preparing nitrogen-doped rutile TiO2 selective photocatalyst |
| CN104176772A (en) * | 2014-09-03 | 2014-12-03 | 北京大学 | High-efficiency hardness removal method based on synthetic titanate nanometer material |
| CN108404924A (en) * | 2018-04-11 | 2018-08-17 | 王彩兰 | It is a kind of that there is visible light-responded composite photo-catalyst preparation method |
-
2009
- 2009-12-08 CN CN2009103110303A patent/CN101723442B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983928A (en) * | 2010-11-10 | 2011-03-09 | 河南师范大学 | Preparation method of titanate nanotube codoped with ions of nitrogen and rare earth elements |
| CN101983928B (en) * | 2010-11-10 | 2013-06-05 | 河南师范大学 | Preparation method of titanate nanotube codoped with ions of nitrogen and rare earth elements |
| CN102115913A (en) * | 2011-01-22 | 2011-07-06 | 西北大学 | Preparation method of titanium dioxide nanotube film |
| CN102115913B (en) * | 2011-01-22 | 2012-08-08 | 西北大学 | Preparation method of titanium dioxide nanotube film |
| CN102962089A (en) * | 2012-11-26 | 2013-03-13 | 杭州电子科技大学 | Method for preparing nitrogen-doped rutile TiO2 selective photocatalyst |
| CN104176772A (en) * | 2014-09-03 | 2014-12-03 | 北京大学 | High-efficiency hardness removal method based on synthetic titanate nanometer material |
| CN108404924A (en) * | 2018-04-11 | 2018-08-17 | 王彩兰 | It is a kind of that there is visible light-responded composite photo-catalyst preparation method |
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