CN101704511B - Preparation method of titanium dioxide nanotube (titanium dioxide nanowire) array heterojunction with visible-light catalytic activity - Google Patents
Preparation method of titanium dioxide nanotube (titanium dioxide nanowire) array heterojunction with visible-light catalytic activity Download PDFInfo
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- CN101704511B CN101704511B CN 200910310111 CN200910310111A CN101704511B CN 101704511 B CN101704511 B CN 101704511B CN 200910310111 CN200910310111 CN 200910310111 CN 200910310111 A CN200910310111 A CN 200910310111A CN 101704511 B CN101704511 B CN 101704511B
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Abstract
The invention relates to a preparation method of a photocatalytic material, in particular to a preparation method of titanium dioxide nanotube (titanium dioxide nanowire) array heterojunction with visible-light catalytic activity. The method can solve the problem that the sunlight utilization of titanium dioxide nanotube/nanowire array is low. The method comprises the following steps: 1. preparing an electrolyte; 2. soaking titanium dioxide nanotube/nanowire array and graphite which are opposite mutually in parallel in the electrolyte to deposit and obtain titanium dioxide nanotube/nanowire array heterojunction; and 3. drying the titanium dioxide nanotube/nanowire array heterojunction obtained in the step 2, then placing in a muffle furnace to calcine for 2h-5h, and cooling the heterojunction along with the furnace to the room temperature to obtain the titanium dioxide nanotube/nanowire array heterojunction with visible-light catalytic activity. The titanium dioxide nanotube/nanowire array heterojunction with visible-light catalytic activity obtained by the method of the invention can be used to degrade methyl orange under the visible light so as to increase the sunlight utilization.
Description
Technical field
The present invention relates to a kind of preparation method of catalysis material.
Background technology
Titanium dioxide (TiO
2) as a kind of important inorganic semiconductor functional material, because it has wet sensitive, air-sensitive, dielectric effect, photoelectric conversion and the superior characteristics such as photocatalysis performance, in fields such as sensor, dielectric material, self-cleaning material, solar cell, photocatalytic degradation pollutants important application prospect is arranged, become both at home and abroad competitively one of focus of research.But titanium dioxide can only utilize the ultraviolet light in the sunshine, and ultraviolet light accounts for the ratio less than 6% of sunshine as the semiconductor of broad stopband, and this has just caused TiO
2The problem that nanotube/linear array is lower to the sunshine utilization rate.
Summary of the invention
Technical problem to be solved by this invention is in order to solve titania nanotube/linear array problem lower to the sunshine utilization rate, a kind of preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity to be provided.
The preparation method that the present invention has the titania nanotube of visible light catalysis activity or titanium dioxide nanowire array hetero-junctions is as follows: one, the preparation of electrolyte: a kind of being dissolved in sodium tungstate, ammonium metavanadate, the potassium bichromate made the electrolyte that concentration is 0.01mol/L~0.05mol/L in the deionized water; Two, with Nano tube array of titanium dioxide or titanium dioxide nanowire array and graphite in parallel immersion electrolyte, take Nano tube array of titanium dioxide or titanium dioxide nanowire array as anode, graphite is negative electrode, then be condition deposit 20min~120min of 1V~10V at voltage, obtain hetero-junctions; Three, after drying up, the hetero-junctions that step 2 is obtained puts into Muffle furnace, then under temperature is 500 ℃~700 ℃ condition, calcining 2h~5h cools to room temperature again with the furnace, namely gets titania nanotube or titanium dioxide nanowire array hetero-junctions with visible light catalysis activity.
The titania nanotube with visible light catalysis activity of gained of the present invention/linear array hetero-junctions is degradable methyl orange under visible light, has improved the utilization rate to sunshine.The titania nanotube with visible light catalysis activity of gained of the present invention/linear array hetero-junctions 2 hours degradation rate maximums to methyl orange under the condition of visible light can reach 46%, are 10 times of visible light catalysis activity of non-loaded titanium dioxide nano thread.
Description of drawings
Fig. 1 is the WO that the specific embodiment 12 gained have visible light catalysis activity
3/ TiO
2The stereoscan photograph of nano-wire array hetero-junctions; Fig. 2 is the WO that the specific embodiment 12 gained have visible light catalysis activity
3/ TiO
2The energy spectrogram of nano-wire array hetero-junctions; Fig. 3 is the WO that the specific embodiment 12 gained have visible light catalysis activity
3/ TiO
2Nano-wire array hetero-junctions, the specific embodiment 13 gained have the V of visible light catalysis activity
2O
5/ TiO
2Nano-tube array hetero-junctions, the Nano tube array of titanium dioxide without any load through 500 ℃ of calcinings, titanium dioxide P25 and through under visible light, degrade the respectively degradation rate curve comparison figure of methyl orange of the titanium dioxide nanowire array without any load of 700 ℃ of calcinings, among the figure
The expression specific embodiment 12 gained have the WO of visible light catalysis activity
3/ TiO
2The nano-wire array hetero-junctions descends at visible light and separates the degradation rate curve of methyl orange,
The expression specific embodiment 13 gained have the V of visible light catalysis activity
2O
5/ TiO
2The nano-tube array hetero-junctions descends at visible light and separates the degradation rate curve of methyl orange,
Expression is separated the degradation rate curve of methyl orange through the Nano tube array of titanium dioxide without any load of 500 ℃ of calcinings in visible light decline,
Expression titanium dioxide P25 descends at visible light and separates the degradation rate curve of methyl orange,
Expression is separated the degradation rate curve of methyl orange through the titanium dioxide nanowire array without any load of 700 ℃ of calcinings in visible light decline.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the preparation method who has the titania nanotube of visible light catalysis activity or titanium dioxide nanowire array hetero-junctions in the present embodiment is as follows: one, the preparation of electrolyte: a kind of being dissolved in sodium tungstate, ammonium metavanadate, the potassium bichromate made the electrolyte that concentration is 0.01mol/L~0.05mol/L in the deionized water; Two, with Nano tube array of titanium dioxide or titanium dioxide nanowire array and graphite in parallel immersion electrolyte, take Nano tube array of titanium dioxide or titanium dioxide nanowire array as anode, graphite is negative electrode, then be condition deposit 20min~120min of 1V~10V at voltage, obtain hetero-junctions; Three, after drying up, the hetero-junctions that step 2 is obtained puts into Muffle furnace, then under temperature is 500 ℃~700 ℃ condition, calcining 2h~5h cools to room temperature again with the furnace, namely gets titania nanotube or titanium dioxide nanowire array hetero-junctions with visible light catalysis activity.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light can reach 46%.
The specific embodiment two: present embodiment and the specific embodiment one are different is that the concentration of electrolyte in the step 1 is 0.02mol/L~0.04mol/L.Other is identical with the specific embodiment one.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 35~46%.
The specific embodiment three: present embodiment and the specific embodiment one are different is that the concentration of electrolyte in the step 1 is 0.03mol/L.Other is identical with the specific embodiment one.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 40%.
The specific embodiment four: present embodiment and the specific embodiment one to three are different is to be condition deposit 30min~100min of 3V~9V at voltage in the step 2.Other is identical with the specific embodiment one to three.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 30~46%.
The specific embodiment five: present embodiment and the specific embodiment one to three are different is to be condition deposit 50min~90min of 4V~7V at voltage in the step 2.Other is identical with the specific embodiment one to three.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 25~46%.
The specific embodiment six: present embodiment and the specific embodiment one to three are different is to be the condition deposit 80min of 5V at voltage in the step 2.Other is identical with the specific embodiment one to three.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 30~46%.
The specific embodiment seven: present embodiment and the specific embodiment one to six are different is to calcine under temperature is 550 ℃~650 ℃ condition in the step 3.Other is identical with the specific embodiment one to six.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 36~46%.
The specific embodiment eight: present embodiment and the specific embodiment one to six are different is to calcine under temperature is 600 ℃ condition in the step 3.Other is identical with the specific embodiment one to six.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 37~46%.
The specific embodiment nine: what present embodiment and the specific embodiment one to eight were different is that calcination time is 2.5h~4.5h in the step 3.Other is identical with the specific embodiment one to eight.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 29~46%.
The specific embodiment ten: what present embodiment and the specific embodiment one were different is that calcination time is 3h in the step 3.Other is identical with the specific embodiment one.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 39~46%.
The specific embodiment 11: present embodiment and the specific embodiment one are different is that sedimentation time in the step 2 is 40min.
The titania nanotube with visible light catalysis activity of gained of the present invention or titanium dioxide nanowire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 33~46%.
The specific embodiment 12: the preparation method of titanium dioxide nanowire array hetero-junctions who has visible light catalysis activity in the present embodiment is as follows: one, the preparation of electrolyte: sodium tungstate is dissolved in makes the electrolyte that concentration is 0.04mol/L in the deionized water; Two, with titanium dioxide nanowire array and graphite in parallel immersion electrolyte, wherein titanium dioxide nanowire array is anode, graphite is negative electrode, is the condition deposit 100min of 10V at voltage then, obtains the titanium dioxide nanowire array hetero-junctions; Three, put into Muffle furnace after the titanium dioxide nanowire array hetero-junctions that step 2 is obtained dries up, then under temperature was 700 ℃ condition, calcining 4h cooled to room temperature again with the furnace, namely gets the WO with visible light catalysis activity
3/ TiO
2The nano-wire array hetero-junctions.
Found out the WO with visible light catalysis activity of present embodiment gained by Fig. 1
3/ TiO
2Nano-wire array hetero-junctions pattern is even, and the vertical distribution of high-sequential is at the titanium matrix surface; The WO with visible light catalysis activity of present embodiment gained as shown in Figure 2
3/ TiO
2The content of W has reached 2.27% in the nano-wire array hetero-junctions, and WO is described
3Success loads on TiO
2On the nano-wire array; The WO with visible light catalysis activity of present embodiment gained as can be seen from Figure 3
3/ TiO
2Nano-wire array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 46%, are non-loaded TiO
210 times of the visible light catalysis activity of nano wire.
The specific embodiment 13: the preparation method of Nano tube array of titanium dioxide hetero-junctions who has visible light catalysis activity in the present embodiment is as follows: one, the preparation of electrolyte: ammonium metavanadate is dissolved in makes the electrolyte that concentration is 0.02mol/L in the deionized water; Two, with Nano tube array of titanium dioxide and graphite in parallel immersion electrolyte, wherein Nano tube array of titanium dioxide is anode, graphite is negative electrode, is the condition deposit 80min of 8V at voltage then, obtains the titanium dioxide nanowire array hetero-junctions; Three, put into Muffle furnace after the Nano tube array of titanium dioxide hetero-junctions that step 2 is obtained dries up, then under temperature was 500 ℃ condition, calcining 3h cooled to room temperature again with the furnace, namely gets the V with visible light catalysis activity
2O
5/ TiO
2The nano-tube array hetero-junctions.
The V with visible light catalysis activity of gained of the present invention
2O
5/ TiO
2Nano-tube array hetero-junctions 2 hours degradation rates to methyl orange under the condition of visible light reach 18%.
Claims (10)
1. the preparation method who has titania nanotube or the titanium dioxide nanowire array hetero-junctions of visible light catalysis activity, the preparation method who it is characterized in that having the titania nanotube of visible light catalysis activity or titanium dioxide nanowire array hetero-junctions is as follows: one, the preparation of electrolyte: a kind of being dissolved in sodium tungstate, ammonium metavanadate, the potassium bichromate made the electrolyte that concentration is 0.01mol/L~0.05mol/L in the deionized water; Two, with Nano tube array of titanium dioxide or titanium dioxide nanowire array and graphite in parallel immersion electrolyte, take Nano tube array of titanium dioxide or titanium dioxide nanowire array as anode, graphite is negative electrode, then be condition deposit 20min~120min of 1V~10V at voltage, obtain hetero-junctions; Three, after drying up, the hetero-junctions that step 2 is obtained puts into Muffle furnace, then under temperature is 500 ℃~700 ℃ condition, calcining 2h~5h cools to room temperature again with the furnace, namely gets titania nanotube or titanium dioxide nanowire array hetero-junctions with visible light catalysis activity.
2. the preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity according to claim 1, the concentration that it is characterized in that electrolyte in the step 1 is 0.02mol/L~0.04mol/L.
3. the preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity according to claim 1, the concentration that it is characterized in that electrolyte in the step 1 is 0.03mol/L.
4. the preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity according to claim 1 and 2 is characterized in that in the step 2 at voltage being condition deposit 30min~100min of 3V~9V.
5. the preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity according to claim 1 and 2 is characterized in that in the step 2 at voltage being condition deposit 50min~90min of 4V~7V.
6. the preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity according to claim 1 and 2 is characterized in that in the step 2 at voltage being the condition deposit 80min of 5V.
7. the preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity according to claim 4 is characterized in that in the step 3 calcining under temperature is 550 ℃~650 ℃ condition.
8. the preparation method with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity according to claim 4 is characterized in that in the step 3 calcining under temperature is 600 ℃ condition.
9. according to claim 1,2 or 7 described preparation methods with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity, it is characterized in that calcination time is 2.5h~4.5h in the step 3.
10. according to claim 1,2 or 7 described preparation methods with titania nanotube or titanium dioxide nanowire array hetero-junctions of visible light catalysis activity, it is characterized in that calcination time is 3h in the step 3.
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Citations (3)
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US6685909B2 (en) * | 1999-10-01 | 2004-02-03 | Battelle Memorial Institute | Nanocrystalline heterojunction materials |
CN101279251A (en) * | 2008-02-27 | 2008-10-08 | 浙江大学 | One-dimensional embedded with hetero-junction photocatalyst intermingle with TiO2 and preparation and use thereof |
CN101514471A (en) * | 2009-02-27 | 2009-08-26 | 哈尔滨工业大学 | Method for preparing TiO2 nanotube array film |
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US6685909B2 (en) * | 1999-10-01 | 2004-02-03 | Battelle Memorial Institute | Nanocrystalline heterojunction materials |
CN101279251A (en) * | 2008-02-27 | 2008-10-08 | 浙江大学 | One-dimensional embedded with hetero-junction photocatalyst intermingle with TiO2 and preparation and use thereof |
CN101514471A (en) * | 2009-02-27 | 2009-08-26 | 哈尔滨工业大学 | Method for preparing TiO2 nanotube array film |
Non-Patent Citations (2)
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