CN108043378B - Nonmetal-doped porous-wall titanium nanotube array visible-light-driven photocatalyst and preparation method and application thereof - Google Patents
Nonmetal-doped porous-wall titanium nanotube array visible-light-driven photocatalyst and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J35/39—
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- B01J35/61—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a nonmetal-doped porous wall titanium nanotube array visible-light-driven photocatalyst and a preparation method and application thereof. The visible light catalyst of the non-metal doped porous wall titanium nanotube array is prepared by a method of calcining a titanium sheet plated with a metal ceramic coating after anodic oxidation, regulating and controlling the parameters of the calcining conditions, and removing part of non-metal elements in a gas form. The photocatalyst has special appearances of a regular independent tube wall array structure, a tube wall multistage pore channel and the like, can realize good visible light response, provides a rapid electron transmission channel and has better adsorption mass transfer performance, the visible light catalytic performance of the photocatalyst is obviously enhanced compared with that of a pure titanium nanotube array with a smooth tube wall, and the utilization efficiency of sunlight and the photoproduction electron hole separation capability are greatly improved. The prepared photocatalyst can be widely applied to the aspects of photocatalysis, photoelectrocatalysis waste water treatment, atmosphere purification and the like.
Description
Technical Field
The invention belongs to the technical field of environment functional materials, and particularly relates to a preparation method of a non-metal doped porous wall titanium nanotube array visible-light-driven photocatalyst and application thereof in environmental management.
Background
The environment and energy are the major problems facing and urgently needing to be solved by people in the 21 st century, and TiO is used2The photocatalytic technique represented by the above is a deep reaction at room temperatureThe solar energy can be directly used as a light source to drive the reaction and other unique properties, thereby becoming an ideal environmental pollution treatment technology and a clean energy production technology. The morphological structure of the semiconductor photocatalyst plays an extremely important role in exerting the maximum catalytic effect. In recent years, TiO with various morphological structures2Materials such as nanotubes, wires, sheets, hollow spheres, and three-dimensional interconnect structures have been developed. Among them, titanium nanotubes have received much attention from researchers due to their large specific surface area, highly controllable structure, and fast electron channel characteristics.
The current methods for preparing titanium nanotubes mainly comprise anodic oxidation, template hydrothermal method and electrostatic spinning. Compared with preparation methods such as template hydrothermal method, electrostatic spinning method and the like, the electrochemical anode oxidation method has simple process and strong operability, and the prepared TiO is2The nanotubes are regularly and uniformly grown and are regularly arranged in a vertical independent array form, and the nanotube array has extremely high nanostructure order, extremely low agglomeration degree, larger specific surface area and stronger adsorption capacity. However, most of the existing anodic oxidation technologies adopt a pure titanium foil electrode as an anode and a platinum sheet as a cathode, so that the cost is high, the prepared pure titanium nanotube array can only be excited by ultraviolet light, the compact tube wall of the pure titanium nanotube array can block light from reaching the inner tube wall, so that the utilization rate of sunlight is further reduced, and the factors greatly limit the large-scale practical application of the nanotube array. Meanwhile, the existing non-metal such as carbon, nitrogen and the like is doped with TiO2The nanotube array technology mostly adopts a doping mode after high-temperature calcination and the like in an atmosphere containing a carbon source or a nitrogen source, so that the requirement on equipment is high, and the instability of doping amount is easily caused. Therefore, the key problem is expected to be solved by using the metal ceramic coating to realize visible light chemical doping and simultaneously construct the multilevel pore canal on the pipe wall.
The method adopts a titanium sheet plated with a titanium carbide/titanium nitride or other metal ceramic coating as a working electrode, and a pure titanium sheet as a cathode to carry out anodic oxidation in fluorine-containing organic electrolyte to obtain an amorphous non-metal doped titanium nanotube array, after the amorphous non-metal doped titanium nanotube array is calcined in the air, part of non-metal escapes in a gas form, a multi-stage pore channel is constructed on the wall of the nanotube, and the simple preparation of the anatase non-metal doped porous wall titanium nanotube array with high catalytic activity is synchronously realized by adjusting the parameters of calcination conditions. Due to the existence of the multi-stage pore channel structure, the nonmetal-doped titanium nanotube with the porous tube wall is further beneficial to the adsorption and mass transfer of reactants, and simultaneously, incident light can enter the inside of the tube through the multi-stage pore channel of the tube wall, so that the light utilization rate of the inner surface of the nanotube array is greatly improved, and on the other hand, the absorption range of the nonmetal elements on sunlight is expanded by uniformly doping the nonmetal elements, and the photocatalysis efficiency of the nonmetal-doped titanium nanotube is further improved. The preparation method adopted by the invention provides a new idea for preparing the novel visible light activated nanotube array material.
Disclosure of Invention
The invention aims to overcome the defects that the cost of a noble metal electrode adopted by the existing anodic oxidation technology is high, a pure titanium nanotube array only responds to ultraviolet light, the tube wall is compact, the sunlight utilization rate is low, and the equipment requirement is high and the doping amount is unstable in the non-metal post-doping modification technology, and provides a simple preparation method of a non-metal doped porous wall titanium nanotube array visible light catalyst and application thereof in environmental management.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nonmetal-doped porous wall titanium nanotube array visible-light-driven photocatalyst is characterized in that the catalyst is a porous wall nanotube array and has visible-light response. The nonmetal doping is realized by taking a pure titanium sheet plated with metal ceramic coatings such as titanium carbide/titanium nitride and the like as a working electrode and a pure titanium sheet as a cathode and carrying out anodic oxidation in fluorine-containing organic electrolyte, the photocatalyst is placed in a muffle furnace after the anodic oxidation and calcined in the air atmosphere, and part of carbon/nitrogen escapes in a gas form, so that a multistage pore channel is constructed on the tube wall of the nanotube. By adjusting the parameters of the calcination conditions, the doping amount and the size of the pore channel are synchronously adjusted, and the nonmetal-doped porous wall titanium nanotube array with visible light response is prepared.
A preparation method of a non-metal doped porous wall titanium nanotube array visible light catalyst comprises the following steps:
(1) pretreatment: taking a pure titanium sheet coated with a metal ceramic coating with the thickness of 5-10 microns, sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water for ultrasonic treatment, and drying the pure titanium sheet at room temperature in the air to obtain a pretreated pure titanium sheet coated with the metal ceramic coating;
(2) anodic oxidation: adopting a two-electrode system, wherein the cathode is a pure titanium sheet, the anode is the pretreated pure titanium sheet plated with the metal ceramic coating obtained in the step (1), and the electrolyte is ammonium fluoride (NH)4F) And a solution of deionized water in Ethylene Glycol (EG); carrying out anodic oxidation under a direct current constant voltage without maintaining the temperature of the electrolyte and stirring; after reaction, the mixture is placed into absolute ethyl alcohol to be soaked for 20-40 min and then is naturally dried at room temperature to obtain amorphous nonmetal-doped TiO2A nanotube array; the NH4The concentration of F is 0.3wt% -0.7 wt%; the volume of the deionized water is 1-3 vol%; the volume of the electrolyte is 55-65 mL;
(3) preparing an anatase nonmetal-doped porous wall titanium nanotube array: doping amorphous nonmetal with TiO2And (3) placing the nanotube array in a muffle furnace for high-temperature calcination in an air atmosphere to obtain the anatase nonmetal-doped porous wall titanium nanotube array.
In the above method, in step (1), the cermet coating includes a titanium carbide coating, a titanium nitride coating or a titanium carbonitride coating; the thickness of the coating is 5-20 mu m, and the mass fraction of the non-metallic elements is not less than 10%;
the ultrasonic cleaning time is 15-30 min, the drying temperature at room temperature is 20-35 ℃, and the drying time is 1-3 h.
In the method, in the step (2), the effective area of the cathode pure titanium sheet is 350-450 mm2(the back is covered by adhesive tape), the effective area of the pure titanium sheet with the anode plated with the metal ceramic coating is 2 multiplied by 350-450 mm2(ii) a The distance between the cathode and the anode is 1-4 cm.
In the method, in the step (2), the anodic oxidation voltage range is 30-90V, the oxidation time is 1-4 h, the anodic oxidation temperature at room temperature is 20-30 ℃, the temperature of the electrolyte does not need to be maintained, and the stirring speed of stirring is 30-50 r/min.
In the method, in the step (2), the drying temperature at room temperature is 20-35 ℃, and the drying time is 10-20 h.
In the method, in the step (3), the calcination temperature is 400-600 ℃, the calcination time is 1-4 h, and the temperature rise rate is 1-5 ℃/min.
In the above method, the calcination method specifically comprises: the temperature raising procedure comprises the steps of raising the temperature from room temperature to 240-260 ℃ at the speed of 2-4 ℃/min, keeping the temperature constant at 240-260 ℃ for 25-35 min, raising the temperature to 400-600 ℃ at the speed of 0.5-1.5 ℃/min, keeping the temperature constant for 1-4 h, and finally lowering the temperature to room temperature at the speed of 1-5 ℃/min.
A non-metal doped porous wall titanium nanotube visible light photocatalyst is applied to wastewater treatment or atmosphere purification.
The invention improves and innovates on the basis of the prior anodic oxidation technology, adopts a two-electrode system, respectively takes a pure titanium sheet and the pure titanium sheet plated with metal ceramic coatings (TiC, TiN and the like) in equal area as a cathode and an anode for anodic oxidation, then calcines the titanium sheet in the air atmosphere, and builds a multilevel pore canal structure on the tube wall by utilizing the gasification of partial nonmetal. By adjusting the parameters of the calcining conditions, the simple preparation of the anatase nonmetal-doped porous wall titanium nanotube array with high catalytic activity is synchronously realized. The photocatalyst has larger specific surface area, higher light utilization rate and adsorption mass transfer efficiency, and the visible light catalytic activity of the photocatalyst is greatly improved.
Compared with the prior art, the invention has the following advantages:
the preparation method has the advantages of simple operation, low cost, synchronous realization of in-situ doping of the visible light response elements and construction of the multistage duct of the duct wall and the like, and has more regular and uniform appearance, more abundant duct structures and high light utilization rate compared with the visible light response nanotube array prepared by other methods. Therefore, the titanium nanotube array has higher photocatalytic activity under visible light compared with the traditional titanium nanotube array. The catalyst can be widely applied to the aspects of treating waste water by photocatalysis or photoelectrocatalysis, purifying atmosphere and the like.
Drawings
FIG. 1 is an XRD pattern of a visible light catalyst of a non-metal doped porous wall titanium nanotube array according to the present invention;
FIG. 2a is a FE-SEM of the top of the visible light catalyst of the nitrogen-doped porous wall titanium nanotube array of the present invention; FIG. 2b is a FE-SEM image of the sidewall of the visible-light-induced photocatalyst of the nitrogen-doped porous titanium nanotube array of the present invention;
FIG. 3a is a FE-SEM of the top of the visible light catalyst of the carbon-doped porous wall titanium nanotube array of the present invention; FIG. 3b is a FE-SEM image of the sidewall of the visible light catalyst of the carbon-doped porous titanium nanotube array of the present invention;
FIG. 4 shows the UV-visible diffuse reflectance spectra DRS of the non-metal doped porous wall titanium nanotube array photocatalyst and pure titanium nanotube array photocatalyst of the present invention;
FIG. 5 is a graph showing the visible light degradation effect of the carbon-doped porous titanium nanotube array photocatalyst and the pure titanium nanotube array photocatalyst on DBP.
FIG. 6 is a graph showing the visible light degradation effect of the nitrogen-doped porous wall titanium nanotube array photocatalyst and the pure titanium nanotube array photocatalyst on DBP.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
(1) Pretreatment of titanium alloy: taking a pure titanium sheet with a surface of 20mm multiplied by 30mm multiplied by 2mm plated with a coating with the thickness of 10 mu mTiN, sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 20min, and drying at room temperature.
(2) Anodic oxidation: adopts a two-electrode system, the cathode is a pure titanium sheet (the effective area is 400 mm)2) The anode is a pure titanium sheet which is treated in the step (1) and is plated with TiN coating, and the area to be anodized is 2 x 400mm2The distance between the two electrodes is 3cm, and the electrolyte is 0.5 wt% NH4F、2vol％H260mL of ethylene glycol solution of O. Oxidizing for 3 hours under the constant voltage of 70V direct current,the initial temperature of the electrolyte was 20 ℃. Soaking the mixture in absolute ethyl alcohol for 20-40 min, and naturally drying the mixture at room temperature to obtain amorphous N-doped TiO2An array of nanotubes.
Example 2
(1) Pretreatment of titanium alloy: taking a pure titanium sheet with a surface of 20mm multiplied by 30mm multiplied by 2mm plated with a coating with the thickness of 10 mu mTiC, sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 20min, and drying at room temperature.
(2) Anodic oxidation: adopts a two-electrode system, the cathode is a pure titanium sheet (the effective area is 400 mm)2) The anode is a pure titanium sheet plated with the TiC coating after the treatment of the step (1), and the area to be anodized is 2 x 400mm2The distance between the two electrodes is 3cm, and the electrolyte is 0.5 wt% NH4F、2vol％H260mL of ethylene glycol solution of O. Oxidizing for 3h under the constant voltage of 70V direct current, wherein the initial temperature of the electrolyte is 20 ℃, and the constant temperature is not required to be maintained. Soaking the mixture in absolute ethyl alcohol for 20-40 min, and naturally drying the mixture at room temperature to obtain amorphous C-doped TiO2An array of nanotubes.
Example 3
(1) Preparing an anatase N-doped porous wall titanium nanotube array: amorphous N-doped TiO prepared in example 12The nanotube array is placed in a muffle furnace to be calcined for 2 hours at the high temperature of 500 ℃ in the air atmosphere. The temperature rise procedure is that the temperature is increased from the room temperature to 250 ℃ at the speed of 2 ℃/min, the temperature is kept at 250 ℃ for 30min, then the temperature is increased to 500 ℃ at the speed of 1 ℃/min, the temperature is kept for 2h, and finally the temperature is reduced to the room temperature at the speed of 3 ℃/min, so that the anatase N-doped porous wall titanium nanotube array is obtained and is marked as N-TNTAs.
(2) Preparing an anatase C doped porous wall titanium nanotube array: amorphous C-doped TiO prepared in example 22The nanotube array is placed in a muffle furnace to be calcined for 2 hours at the high temperature of 500 ℃ in the air atmosphere. The temperature rise procedure is that the temperature is increased from the room temperature to 250 ℃ at the speed of 2 ℃/min, the temperature is kept at 250 ℃ for 30min, then the temperature is increased to 500 ℃ at the speed of 1 ℃/min, the temperature is kept for 2h, and finally the temperature is reduced to the room temperature at the speed of 3 ℃/min, so that the anatase N-doped porous wall titanium nanotube array is obtained and is marked as C-TNTAs.
(3) XRD patterns (figure 1) of different photocatalysts show that the prepared non-metal doped porous wall titanium nanotube arrays are all in pure anatase crystalline phase. Elemental analysis (table 1) indicated successful doping of the non-metallic elements N or C. Scanning electron microscopy (FIGS. 2a and 2b, N-TNTAs), (FIGS. 3a and 3b, C-TNTAs) shows the successful preparation of porous wall titanium nanotube array structures. From the UV-Vis diffuse reflection spectrum (figure 4), the prepared non-metal doped porous wall titanium nanotube array has good visible light response.
TABLE 1 elemental analysis of non-metal doped porous wall titanium nanotube array visible light catalyst
Example 4
Evaluation of photocatalytic activity: and (3) adopting a nondegradable organic dibutyl phthalate (DBP) as a model pollutant, and comparing the visible light catalytic activities of different photocatalysts. The photocatalytic degradation reaction is carried out in a self-made photocatalytic reaction device, and the effective illumination area of the catalyst is 400mm2(vertical to the light source), the light intensity of the light source is visible light AM1.5G (100 mW/cm)2) (ii) a The initial concentration of DBP is 5mg/L, and the total volume of the solution is 100 mL; dark adsorption is carried out for 1h before the light source is started; the concentration of remaining DBP in the solution was determined by high performance liquid chromatography. The concentration of the DBP degraded by the catalyst is equal to the original DBP concentration of the solution minus the concentration of the residual DBP in the solution, and the removal rate of the DBP is the ratio of the DBP concentration degraded by the catalyst to the original concentration of the solution. The experimental results show that: both the N-TNTAs and C-TNTAs photocatalysts show higher visible light catalytic activity than pure titanium nanotube arrays (marked as TNTAs) (figures 5 and 6). The degradation effect graphs (fig. 5 and 6) of different photocatalysts on DBP show that the prepared non-metal doped porous wall titanium nanotube array has excellent environmental benefits.
The above examples are only intended to illustrate the technical solution of the present invention and not to be restrictive in strict terms, and it will be understood by those skilled in the art that various changes in the details or forms thereof may be made without departing from the spirit and scope of the present invention as defined in the claims.
Claims (8)
1. A preparation method of a non-metal doped porous wall titanium nanotube array visible-light-induced photocatalyst is characterized in that the non-metal doped porous wall titanium nanotube array visible-light-induced photocatalyst is prepared by a method of carrying out anodic oxidation and then calcining on a titanium sheet plated with a metal ceramic coating, regulating and controlling the parameters of the calcining conditions, and removing partial non-metal elements in a gas form;
the method comprises the following steps:
(1) pretreatment: taking a pure titanium sheet coated with a metal ceramic coating with the thickness of 5-10 microns, sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water for ultrasonic treatment, and drying the pure titanium sheet at room temperature in the air to obtain a pretreated pure titanium sheet coated with the metal ceramic coating;
(2) anodic oxidation: adopting a two-electrode system, wherein the cathode is a pure titanium sheet, the anode is the pretreated pure titanium sheet plated with the metal ceramic coating obtained in the step (1), and the electrolyte is ammonium fluoride (NH)4F) And a solution of deionized water in Ethylene Glycol (EG); carrying out anodic oxidation under a direct current constant voltage without maintaining the temperature of the electrolyte and stirring; after reaction, the mixture is placed into absolute ethyl alcohol to be soaked for 20-40 min and then is naturally dried at room temperature to obtain amorphous nonmetal-doped TiO2A nanotube array; the NH4The concentration of F is 0.3wt% -0.7 wt%; the volume of the deionized water is 1-3 vol%; the volume of the electrolyte is 55-65 mL;
(3) preparing an anatase nonmetal-doped porous wall titanium nanotube array: doping amorphous nonmetal with TiO2Placing the nanotube array in a muffle furnace for high-temperature calcination in an air atmosphere to obtain an anatase nonmetal-doped porous wall titanium nanotube array;
in the step (3), the calcining temperature is 400-600 ℃, the calcining time is 1-4 h, and the heating rate is 1-5 ℃/min.
2. The method for preparing the visible light catalyst of the non-metal doped porous wall titanium nanotube as claimed in claim 1, wherein in the step (1), the cermet coating comprises a titanium carbide coating, a titanium nitride coating or a titanium carbonitride coating; the thickness of the coating is 5-20 mu m, and the mass fraction of the non-metallic elements is not less than 10%;
the ultrasonic cleaning time is 15-30 min, the drying temperature at room temperature is 20-35 ℃, and the drying time is 1-3 h.
3. The method for preparing the nonmetal-doped porous titanium nanotube visible light catalyst according to claim 1, wherein in the step (2), the effective area of the cathode pure titanium sheet is 350-450 mm2The effective area of the pure titanium sheet with the anode plated with the metal ceramic coating is 2 multiplied by 350-450 mm2(ii) a The distance between the cathode and the anode is 1-4 cm.
4. The preparation method of the non-metal doped porous wall titanium nanotube visible light catalyst according to claim 1, wherein in the step (2), the anodic oxidation voltage is in a range of 30-90V, the oxidation time is 1-4 h, the anodic oxidation temperature at room temperature is 20-30 ℃, the temperature of the electrolyte is not required to be maintained, and the stirring speed is 30-50 r/min.
5. The preparation method of the nonmetal-doped porous wall titanium nanotube visible light catalyst according to claim 1, wherein in the step (2), the drying temperature at room temperature is 20-35 ℃, and the drying time is 10-20 h.
6. The preparation method of the nonmetal doped porous wall titanium nanotube visible light catalyst according to claim 1, wherein the calcination is carried out by the following specific method: the temperature raising procedure comprises the steps of raising the temperature from room temperature to 240-260 ℃ at the speed of 2-4 ℃/min, keeping the temperature constant at 240-260 ℃ for 25-35 min, raising the temperature to 400-600 ℃ at the speed of 0.5-1.5 ℃/min, keeping the temperature constant for 1-4 h, and finally lowering the temperature to room temperature at the speed of 1-5 ℃/min.
7. The visible light catalyst of the non-metal doped porous wall titanium nanotube prepared by the preparation method of any one of claims 1 to 6.
8. The non-metal doped porous wall titanium nanotube visible light photocatalyst of claim 7, applied to wastewater treatment or atmospheric purification.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101204649A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院金属研究所 | Process for preparing cationic nanotube array intermingling titanium oxide |
| CN101814375A (en) * | 2009-02-25 | 2010-08-25 | 清华大学 | Preparation method of nitrogen-doped titanium dioxide nano line electrode |
| CN101891146A (en) * | 2010-07-01 | 2010-11-24 | 淮阴工学院 | Preparation method of magnetic-doped titanium dioxide nanotube |
| CN101922037A (en) * | 2010-09-26 | 2010-12-22 | 武汉大学 | Method for preparing nitrogen-doped titanium dioxide nanotube array |
| CN102260897A (en) * | 2011-06-13 | 2011-11-30 | 武汉科技大学 | Titanium dioxide nanotube array film and preparation method thereof |
| CN102553626A (en) * | 2011-12-29 | 2012-07-11 | 复旦大学 | Preparation method of carbon-nitrogen-codoped TiO2 nano catalysis material |
| CN103985563A (en) * | 2014-04-10 | 2014-08-13 | 东南大学 | Lithium intercalation manganese dioxide-titanium nitride nanotube composite material and preparing method and application thereof |
| EP3081675A1 (en) * | 2015-04-17 | 2016-10-19 | Industry-Academic Cooperation Foundation, Yonsei University | Nanowire bundle array and method for manufacturing the same |
| WO2016183574A1 (en) * | 2015-05-14 | 2016-11-17 | Uwe Bauer | Systems and methods for controlling the degradation of degradable materials |
| CN106345441A (en) * | 2016-08-25 | 2017-01-25 | 华南理工大学 | Mesoporous-wall titanium nanotube photocatalyst and preparation method and application thereof |
| CN106917128A (en) * | 2017-03-10 | 2017-07-04 | 北京工业大学 | A kind of tin molybdenum codope titanium dioxide nanotube array electrode and preparation method |
-
2017
- 2017-10-09 CN CN201710927973.3A patent/CN108043378B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101204649A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院金属研究所 | Process for preparing cationic nanotube array intermingling titanium oxide |
| CN101814375A (en) * | 2009-02-25 | 2010-08-25 | 清华大学 | Preparation method of nitrogen-doped titanium dioxide nano line electrode |
| CN101891146A (en) * | 2010-07-01 | 2010-11-24 | 淮阴工学院 | Preparation method of magnetic-doped titanium dioxide nanotube |
| CN101922037A (en) * | 2010-09-26 | 2010-12-22 | 武汉大学 | Method for preparing nitrogen-doped titanium dioxide nanotube array |
| CN102260897A (en) * | 2011-06-13 | 2011-11-30 | 武汉科技大学 | Titanium dioxide nanotube array film and preparation method thereof |
| CN102553626A (en) * | 2011-12-29 | 2012-07-11 | 复旦大学 | Preparation method of carbon-nitrogen-codoped TiO2 nano catalysis material |
| CN103985563A (en) * | 2014-04-10 | 2014-08-13 | 东南大学 | Lithium intercalation manganese dioxide-titanium nitride nanotube composite material and preparing method and application thereof |
| EP3081675A1 (en) * | 2015-04-17 | 2016-10-19 | Industry-Academic Cooperation Foundation, Yonsei University | Nanowire bundle array and method for manufacturing the same |
| WO2016183574A1 (en) * | 2015-05-14 | 2016-11-17 | Uwe Bauer | Systems and methods for controlling the degradation of degradable materials |
| CN106345441A (en) * | 2016-08-25 | 2017-01-25 | 华南理工大学 | Mesoporous-wall titanium nanotube photocatalyst and preparation method and application thereof |
| CN106917128A (en) * | 2017-03-10 | 2017-07-04 | 北京工业大学 | A kind of tin molybdenum codope titanium dioxide nanotube array electrode and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| "Nanostructured Carbon-Doping Anodic TiO2 from TiC and Its Photoelectrochemical Properties";Xiaoli Cui et al.;《Journal of Nanoscience and Nanotechnology》;20071231;第7卷;第3140-3145页 * |
| "氮掺杂对二氧化钛光催化性能的影响";黄晶晶等;《无机盐工业》;20130910;第45卷(第9期);第58-61页 * |
| "阳极氧化TiN薄膜制备N掺杂纳米TiO2薄膜及其可见光活性";余志勇等;《物理化学学报》;20090115;第25卷(第1期);第35-40页 * |
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