CN100503035C - Non-metal N doped one-dimensional nano-structured Ti0* visible light catalyst and method for producing the same - Google Patents
Non-metal N doped one-dimensional nano-structured Ti0* visible light catalyst and method for producing the same Download PDFInfo
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- CN100503035C CN100503035C CNB200710071316XA CN200710071316A CN100503035C CN 100503035 C CN100503035 C CN 100503035C CN B200710071316X A CNB200710071316X A CN B200710071316XA CN 200710071316 A CN200710071316 A CN 200710071316A CN 100503035 C CN100503035 C CN 100503035C
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Abstract
The invention discloses visible light catalyst of one dimension nanometer structure TiO<SUB>2</SUB> adulterated with non-metal N, which is prepared with the following method: (1) with hydro-thermal method, nanometer TiO<SUB>2</SUB> powder, TiO<SUB>2</SUB> colloid or Ti(OH)<SUB>4</SUB> and alkaline solution is mixed to form mixed suspension for water-thermal reaction; (2) after water-thermal reaction is finished, cooling is adopted, sediment is filtered and cleaned, and then white hydrogen titanium acid is realized; (3) hydrogen titanium acid, doping nitrogen source and water is mixed to form mixed suspension, ultrasound treatment is conducted after stirring, and then uniform mixture of hydrogen titanium acid and doping nitrogen source is realized after drying; (4) uniform mixture of hydrogen titanium acid and doping nitrogen source is calcinated and then visible light catalyst of one dimension nanometer structure TiO<SUB>2</SUB> adulterated with non-metal N is realized. Catalyst provided by the invention has one dimension structure and lavish active point position and can accelerate mass transfer of pollutant to catalyst, and therefore photocatalysis rate is improved; special one dimension structure and non-nitrogen metal adulteration of the invention lead to good visible-light catalytic activity.
Description
Technical field
The present invention relates to a kind of nano-TiO that is applied to room air pollution control field
2Catalyst relates in particular to a kind of non-metal N doped one-dimensional nano-structured TiO
2Visible light catalyst and preparation method thereof.
Background technology
The room air pollution degree generally exceeds outdoor 5～10 times, and people had 80～90% times to spend indoor, and to a certain extent, effect of air pollution on human health is mainly indoor.The investigation that China Association for Standardization provides shows: 60% disease is caused by room air pollution.In the latter stage nineties, along with the high speed development of the raising, particularly building materials industry of domestic housing reform and national life level, the rise of fitting-up craze has been become the main mode of indoor pollution by the pollution that ornament materials caused.
Under the present living conditions of China, the rate of curing the disease and the death rate that are caused by room air are very high, major pollutants in the room air have nitrogen oxide, sulfide, formaldehyde and benzene series thing, wherein the pollution of the formaldehyde that is caused by finishing material, benzene series thing VOCs (VOCs) such as (benzene,toluene,xylenes) has become the main pollution factor of present room air.
Remove airborne VOCs, usually adopt and ventilate, or with charcoal absorption and catalytic oxidation decomposition method, these measure meetings cause secondary pollution or purification efficiency not high.That photocatalysis technology has is nontoxic, reaction condition is gentle, selectivity is little, the mineralization rate advantages of higher, at degradation of contaminant, especially the organic matter aspect more and more is subject to people's attention, and has become hot research in recent years gradually, and more and more demonstrates its broad application prospect.
Yet as catalysis material, TiO
2Forbidden band broad (3.2eV), not response only can absorb the ultraviolet light less than 387nm, to solar energy utilization ratio low (about 3～5%) in visible-range; The recombination rate height of carrier, quantum yield is low, causes photocatalysis efficiency lower, these two defective effects its effective utilization to sunshine, restricted its application aspect room air improvement.Though to TiO
2Carry out metal-dopedly making it that visible light-responded preferably characteristic is arranged, but doping metals can cause TiO
2Heat endurance descend, increase in the complex centre of carrier or need expensive ion implantation device.
Along with calendar year 2001 Asahi (R.Asahi, T.Morikawa, T.Ohwahi, K.Aoki, " Visible-Light Photocatalysis in Nitrogen-doped Titanium Oxides " (" Science " 2001,293:269～271) of Y.Taga replace the TiO of the nitrogen doping of Lattice Oxygen about nitrogen on Science
2-XN
XMake delivering of its paper not reducing under the photoactive prerequisite of ultraviolet, opened TiO with visible light activity
2The prelude of nonmetal doping.
Publication number is that (denomination of invention is: a kind of nitrogen adulterated TiOx mesoporous photocatalytic material and preparation method thereof) announced nitrogen adulterated TiOx mesoporous photocatalytic preparation methods for the patent documentation of CN1274410C, adopting titanium alkoxide and thiocarbamide is the synthetic titanium base presoma of raw material, calcine in the ammonia atmosphere with this presoma again, obtained having visible light-responded mesoporous nitrogen adulterated TiOx photochemical catalyst.But the catalyst of this method preparation does not have one-dimentional structure.Publication number is the nanometer rutile TiO mutually that the patent documentation (denomination of invention is: the nano oxidized titanium catalyst and the synthetic method of sulphur and the codope of nitrogen anion) of CN1562461 provides the codope of a kind of sulphur nitrogen anion
2Visible light catalyst and synthetic method, adopt hydro-thermal and ammonia nitrogenize to synthesize the nano-TiO of sulphur nitrogen codope
2Visible light catalyst, its degraded to the organic dyestuff methylene blue are better than the nano-titanium oxide of sulphur or the doping of nitrogen list, and TiO
2Be rutile-type.But catalyst does not possess one-dimentional structure yet in this technology.Publication number is that (denomination of invention is: the preparation method of one-dimensional single crystal titanium dioxide nano material) disclose a kind of method that adopts hydro-thermal in conjunction with subsequent treatment, synthesized one-dimensional single crystal TiO for the patent documentation of CN1699636
2, but this material only has response to ultraviolet light, can not utilize visible light degraded environmental contaminants.
Summary of the invention
The invention provides a kind of high activity non-metallic nitrogen intermingle with one-dimensional structure TiO that can be used in excited by visible light
2Photochemical catalyst and preparation method.
A kind of non-metal N doped one-dimensional nano-structured TiO
2Visible light catalyst makes by the following method:
(1) adopts hydro-thermal method, with nano-TiO
2Powder, TiO
2Colloid or Ti (OH)
4Be mixed with mixing suspension with aqueous slkali, in autoclave, 60～300 ℃ (preferred 150 ℃) carry out hydro-thermal reaction 3～168h (preferred 48h);
Described aqueous slkali is NaOH or KOH solution, and the molar concentration of aqueous slkali is 1～20mol/L.
Compactedness when carrying out hydro-thermal reaction, promptly to account for the ratio of autoclave liner volume be 10～90% to the volume of reaction mass.
Nano-TiO
2Powder, TiO
2Colloid or Ti (OH)
4The consumption and the relation of aqueous slkali consumption end product is not had influence substantially, so aqueous slkali can use in right amount according to actual conditions, aqueous slkali can be with nano-TiO at least
2Powder, TiO
2Colloid or Ti (OH)
4Soak into.
(2) after hydro-thermal reaction finished, cooling leached sediment, and sediment is used acid solution and the washed with de-ionized water of 0.01～2mol/L respectively, promptly obtained the hydrogen metatitanic acid of white;
The used acid solution of washing and precipitating thing is hydrochloric acid, nitric acid or sulfuric acid solution.
(3) hydrogen metatitanic acid, doping nitrogen source and solvent are mixed with mixing suspension, ultrasonic being uniformly dispersed adopted in the back that stirs, and 40～150 ℃ of dryings obtain the homogeneous mixture of hydrogen metatitanic acid and doping nitrogen source;
Described doping nitrogen source is urea, ethamine, methylamine, ammonium carbonate, carbonic hydroammonium, ammonium sulfate, ammonium chloride, ammonium fluoride, guanidine carbonate, guanidine hydrochloride, aniline or acetamide.
Described hydrogen metatitanic acid and doping nitrogen source molar ratio are 1:(0.25～8).
Described non-metal N doped one-dimensional nano-structured TiO
2Middle nitrogen doping is 0.1～5.0%.
Solvent described in the mixing suspension is water or ethanol, and water or ethanol can volatilize in the drying in later stage, and is therefore little to the final products performance impact, and water or consumption of ethanol make reaction system be convenient to disperse and stir at least.
The purpose of 40～150 ℃ of dryings is to make the homogeneous mixture of hydrogen metatitanic acid and doping nitrogen source be unlikely to thickness, generally is to be dried to powdery, is beneficial to next step calcining.
(4) with the homogeneous mixture of hydrogen metatitanic acid and doping nitrogen source, under aerobic or oxygen free condition, 300～650 ℃ of calcining 0.3～8h obtain non-metal N doped one-dimensional nano-structured TiO
2Visible light catalyst.
Described non-metal N doped one-dimensional nano-structured TiO
2The crystal formation of visible light catalyst is Detitanium-ore-type or rutile-type.
Described non-metal N doped one-dimensional nano-structured TiO2 visible light catalyst form comprises nano wire, nanotube or nanometer band, and the order of magnitude of length is at nanometer and micron, and diameter is at 5～100nm.
Non-metal N doped one-dimensional nano-structured TiO of the present invention
2Visible light catalyst is with nano-TiO
2Powder, TiO
2Colloid or Ti (OH)
4, concentrated alkali solution and doping nitrogen source be primary raw material, the utilization hydrothermal technique obtains final products by acidifying, washing and subsequent heat treatment.
Preparation method's of the present invention is to introduce the nonmetal doping source in the calcining post processing, and making end product is the visible light-responded doped one-dimensional nano-structured TiO of nitrogen
2, and its activity is better than granular nitrogen dopen Nano TiO
2Prior art also can be prepared one-dimensional nano structure TiO
2, but do not have the visible light catalytic performance.
From the angle of photocatalysis effect, described non-metal N doped one-dimensional nano-structured TiO
2In the process of degraded toluene, the non-secondary pollution thing generates, and has all generated water and carbon dioxide, and in humidity, under the identical condition of conditions such as oxygen concentration, its visible light catalytic effect is granular nitrogen doped Ti O
21.2～3.0 times.Above-mentioned catalyst of while photocatalysis effect in the use of continuous 8～48h remains stable, does not find deactivation phenomenom.
The improvement of indoor air pollutants as the reaction excitaton source, is converted into chemical energy with visible light with indoor light source, is used, and therefore greatly reduces processing cost, is a kind of energy-conserving and environment-protective technology.One-dimentional structure TiO
2Have abundant avtive spot and specific area, can improve the light-catalyzed reaction performance.With nonmetal nitrogen intermingle with one-dimensional structure TiO
2It is not long service life that photocatalyst applications has solved general photochemical catalyst in the improvement of indoor air pollutants, the problem that visible light activity is not high enough
Visible light catalyst of the present invention:
(1) mixing of nonmetal nitrogen makes catalysis produce absorption to visible light, and the absorbing wavelength red shift is to 650nm;
(2) realized degraded to the room air typical pollutant, it is high that its specific activity particle nitrogen doped Ti O2 wants;
(3) have special one-dimentional structure and excellent visible light catalytic activity, specific area is big, and the active site position is abundant, helps strengthening the reaction mass transfer process and can accelerate the mass transfer of pollutant to catalysis material, thereby improve photocatalysis efficiency.
The visible light catalyst of visible light catalyst this law preparation of the present invention not only can be used for environmental pollution improvement, and in solar cell, catalytic carrier and optoelectronic device very big application potential is arranged also.
Description of drawings
Fig. 1 is the XRD figure of the catalyst of embodiment 1, shows prepared TiO
2Exist mutually with anatase;
Fig. 2 is that the UV-vis absorption spectrum of embodiment 4 catalyst and P25 compares, and begins that from 600nm absorption is arranged; (the single dimension structure Ti of a-O
2The catalyst of b-embodiment 4 preparations)
Fig. 3 is the XPS collection of illustrative plates of the catalyst of embodiment 2, shows that N exists with anionic form, and doping is 1.1%;
Fig. 4 is the TEM figure of the catalyst of embodiment 3, shows that catalyst has the 1-dimention nano line structure;
Fig. 5 is embodiment 7 catalyst and particle N doped Ti O
2Visible light catalysis activity relatively, show non-metal N doped one-dimensional nano-structured TiO
2Visible light activity than particle nitrogen doped Ti O
2Want high.(a-particle N doped Ti O
2, the catalyst of b-embodiment 1 preparation)
The specific embodiment
Embodiment 1
With 2.0 gram nano-TiOs
2Powder places the NaOH solution of the 10mol/L of 70ml, continues to stir, and obtains containing TiO
2Mixed solution.Above-mentioned solution is transferred in the 100ml autoclave, and 150 ℃ of constant temperature 24 hours, cooling was inclined the upper strata stillness of night, with 0.5mol/L hydrochloric acid solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.With above-mentioned hydrogen metatitanic acid and doped source urea by a certain percentage (1:2) be configured to mixing suspension with water, stir, ultrasonic processing, 80 ℃ of dry 10h obtain the homogeneous mixture of hydrogen metatitanic acid and urea.Said mixture is placed tube furnace, and under oxygen free condition, 400 ℃ of calcining 2h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 1.3%, and crystal formation is an anatase titanium dioxide, and form is a nanotube, about 1 micron of length, diameter is at 8nm.
Under the same conditions, the activity of visible light degraded room air typical pollutant toluene is single nitrogen doping graininess nano-TiO
22.9 times.
The intermittent flow reactor is adopted in the test of degraded room air typical pollutant toluene, and experiment condition is: the initial concentration 1.0mg/m of toluene
3, initial relative humidity 60%, oxygen content 21%, catalyst consumption 0.2g, it is the xenon lamp of 150W that light source adopts power, is the evaluation index of photocatalytic activity with the ratio of the first order reaction apparent speed constant in the photochemical catalytic oxidation process, and visible light activity is with granular nitrogen dopen Nano TiO
2Be benchmark.
Embodiment 2
With 4.5 gram nano-TiOs
2Powder places the KOH solution of the 12mol/L of 80ml, continues to stir, and obtains containing TiO
2Mixed solution.Above-mentioned solution is transferred in the 100ml autoclave, and 130 ℃ of constant temperature 48 hours, cooling was inclined the upper strata stillness of night, with 2.5mol/L sulfuric acid solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.With above-mentioned hydrogen metatitanic acid and doped source ethamine by a certain percentage (1:4) be configured to mixing suspension with water, stir certain hour, ultrasonic processing, 100 ℃ of dry 8h obtain the homogeneous mixture of hydrogen metatitanic acid and ethamine.Said mixture is placed tube furnace, and under aerobic conditions, 500 ℃ of calcining 1.5h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 1.8%, and crystal formation is an anatase titanium dioxide, and form is about 1.5 microns an of nanowire length, and diameter is at 5nm.(adopt the experimental condition of embodiment 1) under the same conditions, the activity of visible light degraded room air typical pollutant toluene is granular nitrogen dopen Nano TiO
22.1 times.
Embodiment 3
With 5.0 gram TiO
2Colloid places the NaOH solution of the 15mol/L of 140ml, continues to stir, and obtains containing TiO
2The mixed solution of colloid.Above-mentioned solution is transferred in the 200ml autoclave, and 120 ℃ of constant temperature 48 hours, cooling was inclined the upper strata stillness of night, with 0.2mol/L salpeter solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.With above-mentioned hydrogen metatitanic acid and doped source ammonium carbonate by a certain percentage (1:1) be configured to mixing suspension with water, stir, ultrasonic processing, 60 ℃ of dry 12h obtain the homogeneous mixture of hydrogen metatitanic acid and ammonium carbonate.Said mixture is placed tube furnace, and under aerobic conditions, 550 ℃ of calcining 3h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 0.6%, and crystal formation is an anatase titanium dioxide, and form is about 0.7 micron an of nanowire length, the about 5.5nm of diameter.(adopt the experimental condition of embodiment 1) under the same conditions, the activity of visible light degraded room air typical pollutant toluene is granular nitrogen dopen Nano TiO
21.7 times.
Embodiment 4
With 2.5 gram TiO
2Colloid places the NaOH solution of the 8.0mol/L of 85ml, continues to stir, and obtains containing TiO
2The mixed solution of colloid.Above-mentioned solution is transferred in the 100ml autoclave, and 220 ℃ of constant temperature 12 hours, cooling was inclined the upper strata stillness of night, with 0.5mol/L salpeter solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.With above-mentioned hydrogen metatitanic acid and doped source guanidine carbonate by a certain percentage (1: 8) be configured to mixing suspension with water, stir certain hour, ultrasonic processing, 70 ℃ of dry 7h obtain the homogeneous mixture of hydrogen metatitanic acid and guanidine carbonate.Said mixture is placed tube furnace, and under oxygen free condition, 350 ℃ of calcining 4h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 2.5%, and crystal formation is an anatase titanium dioxide, and form is about 1.3 microns of a nanometer strip length, and diameter is at 9.5nm.(adopt the experimental condition of embodiment 1) under the same conditions, the activity of visible light degraded room air typical pollutant toluene is granular nitrogen dopen Nano TiO
22.4 times.
Embodiment 5
With 3.5 gram TiO
2Colloid places the KOH solution of the 14.0mol/L of 100ml, continues to stir, and obtains containing Ti (OH)
4Mixed solution.Above-mentioned solution is transferred in the 200ml autoclave, and 110 ℃ of constant temperature 40 hours, cooling was inclined the upper strata stillness of night, with 5.5mol/L salpeter solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.With above-mentioned hydrogen metatitanic acid and doped source acetamide by a certain percentage (1:2.5) be configured to mixing suspension with water, stir certain hour, ultrasonic processing, 100 ℃ of dry 6h obtain the homogeneous mixture of hydrogen metatitanic acid and acetamide.Said mixture is placed tube furnace, and under aerobic conditions, 450 ℃ of calcining 3h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 1.5%, and crystal formation is an anatase titanium dioxide, and form is a nanotube length
Micron, diameter is at 12.0nm.(adopt the experimental condition of embodiment 1) under the same conditions, as seen,
The activity of room air typical pollutant toluene is granular nitrogen dopen Nano TiO
21.5 times.
Embodiment 6
With 6.0 gram Ti (OH)
4Place the 11.0mol/LKOH solution of 130ml, continue to stir, obtain containing Ti (OH)
4Mixed solution.Above-mentioned solution is transferred in the 200ml autoclave, and 250 ℃ of constant temperature 12 hours, cooling was inclined the upper strata stillness of night, with 1.0mol/L salpeter solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.With above-mentioned hydrogen metatitanic acid and doped source guanidine hydrochloride by a certain percentage (1:3) be configured to mixing suspension with water, stir certain hour, ultrasonic processing, 80 ℃ of dry 8h obtain the homogeneous mixture of hydrogen metatitanic acid and guanidine hydrochloride.Said mixture is placed tube furnace, and under aerobic conditions, 600 ℃ of calcining 1h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 1.6%, and crystal formation is a rutile-type, and form is about 1.5 microns of a nanometer strip length, and diameter is at 5.5nm.(adopt the experimental condition of embodiment 1) under the same conditions, the activity of visible light degraded room air typical pollutant toluene is granular nitrogen dopen Nano TiO
22.5 times.
Embodiment 7
With 3.5 gram TiO
2Powder places the KOH solution of the 13.0mol/L of 150ml, continues to stir, and obtains containing TiO
2The mixed solution of powder.Above-mentioned solution is transferred in the 100ml autoclave, and 200 ℃ of constant temperature 18 hours, cooling was inclined the upper strata stillness of night, with 0.8mol/L hydrochloric acid solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.With above-mentioned hydrogen metatitanic acid and doped source methylamine by a certain percentage (1:4) be configured to mixing suspension with water, stir certain hour, ultrasonic processing, 80 ℃ of dry 8h obtain the homogeneous mixture of hydrogen metatitanic acid and methylamine.Said mixture is placed tube furnace, and under oxygen free condition, 300 ℃ of calcining 4h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 2.5%, and crystal formation is a Detitanium-ore-type, and form is about 1.8 microns an of nanowire length, and diameter is at 6.5nm.(adopt the experimental condition of embodiment 1) under the same conditions, the activity of visible light degraded room air typical pollutant toluene is granular nitrogen dopen Nano TiO
22.7 times.
Embodiment 8
With 4.0 gram Ti (OH)
4Place the NaOH solution of the 8.0mol/L of 50ml, continue to stir, obtain containing Ti (OH)
4Mixed solution.Above-mentioned solution is transferred in the 100ml autoclave, and 250 ℃ of constant temperature 12 hours, cooling was inclined the upper strata stillness of night, with 0.01mol/L salpeter solution and washed with de-ionized water, obtained white depositions hydrogen metatitanic acid.Above-mentioned hydrogen metatitanic acid and doped source sulphur methylamine certain proportion (1:2.5) and water are configured to mixing suspension, stir certain hour, ultrasonic processing, 90 ℃ of dry 6h obtain the homogeneous mixture of hydrogen metatitanic acid and methylamine.Said mixture is placed tube furnace, and under aerobic conditions, 550 ℃ of calcining 1h obtain non-metal N doped one-dimensional nano-structured TiO
2, the nitrogen doping is 0.9%, and crystal formation is that anatase mixes mutually with rutile, and form is about 1.5 microns of a nanometer strip length, and diameter is at 8.0nm.(adopt the experimental condition of embodiment 1) under the same conditions, the activity of visible light degraded room air typical pollutant toluene is granular nitrogen dopen Nano TiO
21.6 times.
Claims (7)
1, a kind of non-metal N doped one-dimensional nano-structured TiO
2Visible light catalyst, preparation by the following method:
(1) adopts hydro-thermal method, with nano-TiO
2Powder, TiO
2Colloid or Ti (OH)
4Be configured to mixing suspension with aqueous slkali, carry out hydro-thermal reaction 3～168h at 60～300 ℃;
(2) after hydro-thermal reaction finished, cooling leached sediment, and sediment is used acid solution and washed with de-ionized water respectively, promptly obtained the hydrogen metatitanic acid of white;
(3) hydrogen metatitanic acid, doping nitrogen source and solvent are configured to mixing suspension, mix, 40～150 ℃ of dryings obtain the homogeneous mixture of hydrogen metatitanic acid and doping nitrogen source;
(4) with 300～650 ℃ of calcinings of homogeneous mixture of hydrogen metatitanic acid and doping nitrogen source, obtain non-metal N doped one-dimensional nano-structured TiO
2Visible light catalyst.
2, non-metal N doped one-dimensional nano-structured TiO as claimed in claim 1
2Visible light catalyst is characterized in that: the described aqueous slkali of step (1) is NaOH or KOH solution, and the molar concentration of aqueous slkali is 1～20mol/L.
3, non-metal N doped one-dimensional nano-structured TiO as claimed in claim 1
2Visible light catalyst is characterized in that: 150 ℃ of the described hydrothermal temperatures of step (1), the reaction time is 48h.
4, non-metal N doped one-dimensional nano-structured TiO as claimed in claim 1
2Visible light catalyst is characterized in that: the described acid solution of step (2) is hydrochloric acid, nitric acid or sulfuric acid solution, and acid solutions is 0.01～2mol/L.
5, non-metal N doped one-dimensional nano-structured TiO as claimed in claim 1
2Visible light catalyst is characterized in that: the described doping nitrogen source of step (3) is urea, ethamine, methylamine, ammonium carbonate, carbonic hydroammonium, ammonium sulfate, ammonium chloride, ammonium fluoride, guanidine carbonate, guanidine hydrochloride, aniline or acetamide.
6, non-metal N doped one-dimensional nano-structured TiO as claimed in claim 1
2Visible light catalyst is characterized in that: described hydrogen metatitanic acid of step (3) and doping nitrogen source molar ratio are 1:(0.25～8).
7, non-metal N doped one-dimensional nano-structured TiO as claimed in claim 1
2Visible light catalyst is characterized in that: the described solvent of step (3) is ethanol or water.
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| CN102728391B (en) * | 2011-04-15 | 2014-08-13 | 河南科技大学 | Sulfur doped titanate nanotube visible light catalyst material and its preparation method |
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| 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 |
| CN103007912B (en) * | 2012-12-12 | 2015-03-11 | 合肥工业大学 | One-dimensional nanometer titania photocatalyst with mica serving as support and preparation method thereof |
| CN103074661B (en) * | 2013-01-07 | 2015-04-15 | 南昌航空大学 | Method for controlling hydrophily and hydrophobicity of array surface of titanium dioxide nanotube |
| CN103342402A (en) * | 2013-07-04 | 2013-10-09 | 浙江科技学院 | Method for degrading methylene blue by using nitrogen-doped oxygen vacancy type TiO2 catalyst |
| CN103464190B (en) * | 2013-09-17 | 2015-12-02 | 中国科学院广州地球化学研究所 | Nitrogen-doped carbon polymer/TiO 2optoelectronic pole and preparation method thereof and application |
| CN103638957A (en) * | 2013-12-03 | 2014-03-19 | 张佳佳 | Photocatalyst material |
| CN104959159A (en) * | 2015-05-21 | 2015-10-07 | 浙江大学 | Nitrogen-doped titanium dioxide film, and preparation method and applications thereof |
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