CN101519233B - Method for degrading organic substances by using photoelectric catalysis of short TiO2 nano-tube array film electrode - Google Patents
Method for degrading organic substances by using photoelectric catalysis of short TiO2 nano-tube array film electrode Download PDFInfo
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- CN101519233B CN101519233B CN2009100482183A CN200910048218A CN101519233B CN 101519233 B CN101519233 B CN 101519233B CN 2009100482183 A CN2009100482183 A CN 2009100482183A CN 200910048218 A CN200910048218 A CN 200910048218A CN 101519233 B CN101519233 B CN 101519233B
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Abstract
The invention relates to a method for degrading organic substances by using photoelectric catalysis of a short TiO nano-tube array film electrode, and belongs to the technical field of environment polThe invention relates to a method for degrading organic substances by using photoelectric catalysis of a short TiO nano-tube array film electrode, and belongs to the technical field of environment pol tube length as the electrode, the method has the advantages of low photo-generated charge compound and quick transmission, and shows higher property of degrading the organic substances by photoelecer tube length as the electrode, the method has the advantages of low photo-generated charge compound and quick transmission, and shows higher property of degrading the organic substances by photoelectric catalysis.tric catalysis.lution governance. A cleaned titanium sheet as an anode is placed into an electrolyte solution containing fluorine ions, a platinum electrode as a counter electrode is subjected to anode oxidizing realution governance. A cleaned titanium sheet as an anode is placed into an electrolyte solution containing fluorine ions, a platinum electrode as a counter electrode is subjected to anode oxidizing reaction, the reacted electrolyte solution is subjected to ultrasonic dispersion during the whole anode oxidizing reaction, and the reactants are sintered after the anode oxidization is ended to obtain tction, the reacted electrolyte solution is subjected to ultrasonic dispersion during the whole anode oxidizing reaction, and the reactants are sintered after the anode oxidization is ended to obtain the short TiO2 nano-tube array film electrode. By using the obtained short TiO2 nano-tube array film electrode as a working electrode, Ag-AgCl as a reference electrode and Pt as the counter electrode,he short TiO2 nano-tube array film electrode. By using the obtained short TiO2 nano-tube array film electrode as a working electrode, Ag-AgCl as a reference electrode and Pt as the counter electrode,0.01 to 1 mole of sodium sulfate solution is added into organic pollutant solution, and then the organic pollutants can be degraded. By adopting the firm TiO2 nano-tube array film electrode with short0.01 to 1 mole of sodium sulfate solution is added into organic pollutant solution, and then the organic pollutants can be degraded. By adopting the firm TiO2 nano-tube array film electrode with shorter
Description
Technical field
The present invention relates to the short TiO of a kind of utilization
2The method of nano-tube array film electrode photoelectric catalysis degrading organic belongs to the environmental pollution treatment technology field.
Background technology
Nano-TiO
2Be widely used in organic pollutant in the catalyzed oxidation environment as a kind of good photocatalyst.In recent ten years, TiO
2Be widely used in fields such as textiles, sanitary product, material of construction, coating, and its photochemical stability is good, nontoxic, inexpensive.Calendar year 2001, people such as U.S. scientist Grimes utilize anodised method to prepare TiO in the hydrofluoric acid aqueous solution medium
2Nano-pipe array thin film (Gong D W et al J.Mater.Res. (2001) 16:3331-3334).In this material, photocatalyst TiO
2Nanotube is arranged on the metallic titanium matrix vertical, in good orderly, helps the separation and the transmission of photogenerated charge, as electrode materials, can show the performance of good photoelectric catalysis degrading organic.By changing electrolytical composition in the anodic oxidation, as adopting organic electrolyte, the length that can improve nanotube is to several microns even hundreds of micron.Yet, from the photoelectric catalysis degrading organic pollutant impact of performance, along with TiO
2The increase of nanotube pipe range does not bring the raising of catalytic performance, has caused the decline of nanotube electrode stability on the contrary.Grimes etc. (Grimes, et al (2007) J Phys Chem C 111:14770-14776) studies show that the increase along with pipe range, and the bonding force between bonding force between the tube and tube and nano-tube film layer and the bottom matrix is also corresponding to be weakened.Simultaneously, anodic oxidation prepares in the nanotube process obstruction that the long tube that produces fracture and other residue etc. can be easy to cause nanotube layer in organic electrolyte.These reasons have all reduced long TiO
2The stability of nanometer pipe array electrode has influenced the separation efficiency and the transfer rate of its photogenerated charge, and then has influenced TiO
2The performance of the photoelectric catalysis degrading organic pollutant of nanometer pipe array electrode.The TiO of prior art for preparing
2Nano-tube array, its anode oxidation process carries out under magnetic agitation, the TiO for preparing under agitation condition
2Nanometer pipe array electrode, pipe range is longer, the bonding force of metal titanium and substrate a little less than, this is to cause TiO
2A little less than nanometer pipe array electrode nanotube and the substrate caking power, the poor stability major cause.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of utilization short TiO
2The method of nano-tube array film electrode photoelectric catalysis degrading organic, the preparation pipe range is short, blocky TiO
2Nano-tube array film electrode, the activity of raising photoelectric catalysis degrading organic pollutant.
For achieving the above object, the present invention prepares TiO in anodic oxidation
2In the process of nano-tube array film electrode, carry out ultrasonic method for used anodic oxidation reactions electrolyte solution and disperse,, blocky TiO short with the preparation pipe range
2Nano-tube array film electrode is used for the photoelectric catalysis degrading organic pollutant.
The present invention prepares short TiO
2The concrete grammar of nano-tube array film electrode is:
The titanium sheet that cleaned as anode, is placed the electrolyte solution of fluoride ion, is counter electrode with the platinum electrode, carries out anodic oxidation, and anodic oxidation voltage is controlled at 10-30V.In whole anodic oxidation reactions process, the electrolyte solution of the fluoride ion that reacts to be carried out ultrasonic echography disperse, the reaction times is controlled at 10-60min, and frequency of ultrasonic is controlled between the 25KHz-80KHz; After anodic oxidation is finished, obtain short TiO
2The nano-pipe array thin film sample; Short TiO with gained
2Nano-pipe array thin film samples with water flushing is placed in the baking oven dry, be cooled to room temperature after, again through sintering, obtain short TiO
2Nano-tube array film electrode.
The method of degradable organic pollutant of the present invention is:
With the short TiO behind the sintering
2Nano-pipe array thin film is a working electrode, is reference electrode with Ag-AgCl, is counter electrode with Pt, the metabisulfite solution that adds volumetric molar concentration and be 0.01-1M in organic pollutant solution is as ionogen, and apply bias-voltage 0.4-1.2V, and open light source, organic pollutant is degraded.
The present invention prepares short TiO
2During nano-tube array film electrode, the electrolyte solution of described fluoride ion is a hydrofluoric acid aqueous solution, and wherein the mass percent of fluorion is 0.2-1%, and the compound that constitutes fluorion is a hydrofluoric acid.
Among the present invention, described short TiO
2During nano-pipe array thin film sample sintering, its sintering temperature is 400～700 ℃, and sintering time 0.5-3 hour, sintering atmosphere can be that air atmosphere also can be an oxygen atmosphere.
The short TiO that the present invention prepares
2Nano-tube array film electrode, its pipe range scope is 70-300nm.
Compared with the prior art the method for photoelectric catalysis degrading organic pollutant of the present invention has significant advantage.Owing to prepare TiO in anodic oxidation
2In the process of nanometer pipe array electrode, adopt ultrasonic method to substitute existing stirring method and electrolyte solution is disperseed prepared TiO
2The nanometer pipe array electrode pipe range is short, and pipe combines firmly with substrate, and nanotube surface is smooth, and when being used as photoelectrocatalysielectrode electrode, photogenerated charge is compound lower, transmits sooner, thereby can show the performance of higher photoelectric catalysis degrading organic.Why ultrasonic method can prepare the short and solid orderly TiO of pipe range if substituting existing stirring method
2Nano-pipe array thin film is determined by the distinctive performance of ultra-sonic dispersion.In ultrasonic procedure, the intravital micro-bubble of liquid produces strong vibration with sound pressure variations in the ultrasonic field, and the strong pressure of instantaneous generation and local temperature raise the solution particle is produced the intensive ultrasonic cavitation.This compares with traditional stirring means, ultrasonication can improve electrochemical reaction rates, and the mass transfer in the increase system shortens anodizing time, thereby obtain film thickness weak point, controllable size, high-sequential and directly link to each other, in conjunction with more firm TiO with the metal titanium substrate
2Nano-pipe array thin film.Above-mentioned just reason, the electrode that makes the present invention prepare has the activity of higher photoelectric catalysis degrading organic.The inventive method can be widely used in the processing of all kinds of waste water.
Photoelectric catalysis degrading organic method of the present invention adopts pipe range weak point, blocky TiO
2Nano-pipe array thin film is done electrode, and photogenerated charge is compound low, and transmission is fast, can show the performance of higher photoelectric catalysis degrading organic, can be widely used in the processing of all kinds of waste water.
Description of drawings
Fig. 1 is that the embodiment of the invention 1 is at the short TiO of preparation
2Electric current-time curve in the nano-pipe array thin film process contrasts and is electric current-time curve in the preparation process under the same terms magnetic agitation.
Fig. 2 is the short TiO of the embodiment of the invention 1 preparation
2The stereoscan photograph of nano-tube array (a) is front view, (b) is side-view, (c) utilizes traditional magnetic agitation method to prepare TiO in the reference examples
2The side-view of nano-tube array.
Fig. 3 is the short TiO of the embodiment of the invention 1 preparation
2Nano-pipe array thin film (curve a) with the TiO for preparing with traditional magnetic agitation method
2The photoelectric current curve ratio of nano-pipe array thin film (curve b) in the 1M potassium hydroxide solution.
Fig. 4 is the short TiO of the embodiment of the invention 1 preparation
2Nano-pipe array thin film (curve a) with the photocurrent response curve of the nano-pipe array thin film for preparing with traditional magnetic agitation method (curve b) in different organic solutions.Wherein, (I) be the 10mM glucose solution; (II) be 1mM Potassium Hydrogen Phthalate solution; (III) be the 0.1mM methyl orange solution.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1:
The titanium sheet that cleaned as anode, is got platinized platinum and is assembled into the two electrodes system as counter electrode, and add hydrofluoric acid aqueous solution do ionogen in reaction vessel, make that the mass percent of fluorion reaches 0.5% in the solution, regulating voltage is 20V.In the whole anodic oxidation reactions process electrolyte solution is carried out ultrasonic echography and disperse, ultrasonic frequency 40KHz behind the reaction 30min, stops ultrasonicly, can obtain short TiO
2The nano-pipe array thin film sample.Take off sample, the water flushing is placed in the baking oven dry, to be cooled to room temperature, observe through SEM, and the titanium base TiO2 nano-tube array of preparation, pipe range is the 280nm (see figure 1).Sample sintering in 400 ℃ of air atmospheres was promptly obtained short TiO after 3 hours
2Nano-tube array film electrode can be used as the degraded that photoelectrocatalysielectrode electrode is used for organic pollutant.
With the short TiO behind the sintering
2It is that the methyl orange solution of 20mg/L is as working electrode that nano-tube array film electrode is put into starting point concentration, with Ag-AgCl is reference electrode, and Pt is a counter electrode, adds the 0.01M metabisulfite solution in methyl orange solution, at room temperature apply the 0.5V bias-voltage, adopt ultra violet lamp TiO simultaneously
2Nanotube electrode.Behind the reaction 3h, methyl orange degradation is more than 90%.
In contrast, as anode, platinized platinum is assembled into the two electrodes system as counter electrode with the titanium sheet that cleaned, and adds hydrofluoric acid aqueous solution do ionogen in reaction vessel, makes that the mass percent of fluorion reaches 0.5% in the solution, and regulating voltage is 20V.Whole anode oxidation process adopts magnetic agitation, behind the reaction 30min, takes off sample, and the water flushing is placed in the baking oven dry, to be cooled to room temperature, can obtain titanium base TiO
2Nano-pipe array thin film, pipe range are 500nm (seeing Fig. 1 c).Electrode film behind the sintering 3h, promptly be can be used as the degraded that photoelectrocatalysielectrode electrode is used for organic pollutant in 400 ℃ of air atmospheres.
Fig. 1 has provided preparation TiO under two kinds of different solutions dispersion conditions
2Its electric current-time curve in the nano-pipe array thin film process, as seen from Figure 1, at electric current-time curve that the ultra-sonic dispersion process obtains, the current density value that its current density will obtain far above the magnetic agitation process illustrates under ultrasonication TiO
2The dissolution rate of nanotube layer increases obviously, and this makes TiO
2Nano-tube film pipe layer thickness is shorter.
Fig. 2 has provided two kinds of different dispersion conditions TiO of preparation down
2The stereoscan photograph of nano-tube array (a) is embodiment 1 front view, (b) is embodiment 1 side-view, (c) utilizes traditional magnetic agitation method to prepare TiO in the reference examples
2The side-view of nano-tube array.Scanning electron microscope is PHILIPS, Netherlands, Sirion200 mirror, acceleration voltage 5kV.By 2 figure as seen, arrange high-sequential by the nano-pipe array thin film of ultrasonic method preparation on matrix surface, caliber is 70nm, and pipe range is short to be 280nm.And under the similarity condition, utilize the pipe range of the nano-pipe array thin film that the magnetic agitation method prepares to be 500nm.
Fig. 3 has provided the short TiO for preparing under the embodiment 1 ultra-sonic dispersion condition
2Nano-pipe array thin film (the TiO that curve a) prepares with traditional magnetic agitation method
2The photoelectric current curve ratio of nano-pipe array thin film (curve b) in the 1M potassium hydroxide solution be (curve c is a dark current).As seen from Figure 3, the short TiO for preparing by ultrasonic method
2Nano-pipe array thin film has demonstrated the TiO for preparing than with traditional magnetic agitation method
2The catalytic activity that nano-pipe array thin film is higher.
Fig. 4 has provided the short TiO for preparing under the embodiment 1 ultra-sonic dispersion condition
2Nano-pipe array thin film (the TiO that curve a) prepares with traditional magnetic agitation method
2The photocurrent response curve of nano-pipe array thin film (curve b) in different organic solutions.Wherein, (I) be the 10mM glucose solution; (II) be 1mM Potassium Hydrogen Phthalate solution; (III) be the 0.1mM methyl orange solution.As seen from Figure 4, no matter in which kind of organic solution, the short TiO for preparing by the inventive method
2Nano-pipe array thin film all shows high photocurrent response than the electrode for preparing with traditional magnetic agitation method, thereby shows high photoelectric catalysis degrading organic pollutant activity.
Embodiment 2:
The titanium sheet that cleaned as anode, is got platinized platinum and is assembled into the two electrodes system as counter electrode, and add hydrofluoric acid aqueous solution do ionogen in reaction vessel, make that the mass percent of fluorion reaches 0.2% in the solution, regulating voltage is 30V.In the whole anode oxidation process electrolyte solution is carried out ultrasonic echography and disperse, ultrasonic frequency 25KHz reacted after 1 hour, can obtain short TiO
2The nano-pipe array thin film sample.Take off sample, the water flushing is placed in the baking oven dry, to be cooled to room temperature, observes the titanium base TiO of preparation through SEM
2Nano-tube array, pipe range are 300nm.Sample sintering in 500 ℃ of air atmospheres was promptly obtained short TiO after 0.5 hour
2Nano-tube array film electrode can be used as the degraded that photoelectrocatalysielectrode electrode is used for organic pollutant.
With the short TiO behind the sintering
2It is that the tetracycline of 50mg/L is as working electrode that nano-tube array film electrode is put into starting point concentration, with Ag-AgCl is reference electrode, and Pt is a counter electrode, adds the 1M metabisulfite solution in tetracycline, at room temperature apply the 1.2V bias-voltage, adopt ultra violet lamp TiO simultaneously
2Nanotube electrode.Behind the reaction 3h, tsiklomitsin is degraded more than 85%.
Embodiment 3:
The titanium sheet that cleaned as anode, is got platinized platinum and is assembled into the two electrodes system as counter electrode, and add hydrofluoric acid aqueous solution do ionogen in reaction vessel, make that the mass percent of fluorion reaches 0.7% in the solution, regulating voltage is 10V.In the whole anode oxidation process electrolyte solution is carried out ultrasonic echography and disperse, ultrasonic frequency 80KHz behind the reaction 60min, can obtain short TiO
2The nano-pipe array thin film sample.Take off sample, the water flushing is placed in the baking oven dry, to be cooled to room temperature, observes the titanium base TiO of preparation through SEM
2Nano-tube array, pipe range are 70nm.Sample sintering in 600 ℃ of oxygen atmospheres was promptly obtained short TiO after 3 hours
2Nano-tube array film electrode can be used as the degraded that photoelectrocatalysielectrode electrode is used for organic pollutant.
With the short TiO behind the sintering
2It is that the dihydroxyphenyl propane solution of 15mg/L is as working electrode that nano-tube array film electrode is put into starting point concentration, with Ag-AgCl is reference electrode, and Pt is a counter electrode, adds the 0.05M metabisulfite solution in dihydroxyphenyl propane solution, at room temperature apply the 0.8V bias-voltage, adopt ultra violet lamp TiO simultaneously
2Nanotube electrode.Behind the reaction 2.5h, dihydroxyphenyl propane is degraded more than 85%.
Embodiment 4:
The titanium sheet that cleaned as anode, is got platinized platinum and is assembled into the two electrodes system as counter electrode, and add hydrofluoric acid aqueous solution do ionogen in reaction vessel, make that the mass percent of fluorion reaches 1% in the solution, regulating voltage is 25V.In the whole anode oxidation process electrolyte solution is carried out ultrasonic echography and disperse, ultrasonic frequency 80KHz behind the reaction 10min, can obtain TiO
2The incorporate sample of nano-pipe array thin film and metallic titanium matrix.Take off sample, the water flushing is placed in the baking oven dry, to be cooled to room temperature, and through observing, the synthetic nano-tube film is arranged high-sequential, and pipe range is 200nm.Sample sintering in 700 ℃ of air atmospheres was promptly obtained short TiO after 1 hour
2Nano-tube array film electrode can be used as the degraded that photoelectrocatalysielectrode electrode is used for organic pollutant.
With the short TiO behind the sintering
2It is 10mg/L von Muller's indicator solution that nano-tube array film electrode is put into starting point concentration, is reference electrode with Ag-AgCl, and Pt is a counter electrode, adds the 0.1M metabisulfite solution in von Muller's indicator solution, at room temperature applies the 0.4V bias-voltage, adopts ultra violet lamp TiO simultaneously
2Nanotube electrode.React after 2 hours, von Muller's indicator is degraded more than 75%.
Claims (4)
1. one kind is utilized short TiO
2The method of nano-tube array film electrode photoelectric catalysis degrading organic is characterized in that comprising the steps:
The titanium sheet that 1) will clean places the electrolyte solution of fluoride ion as anode, is counter electrode with the platinum electrode, carries out anodic oxidation, and anodic oxidation voltage is controlled at 10-30V; In whole anodic oxidation reactions process, the electrolyte solution of the fluoride ion that reacts to be carried out ultrasonic echography disperse, the reaction times is controlled at 10-60min, and frequency of ultrasonic is controlled between the 25KHz-80KHz; After anodic oxidation is finished, obtain short TiO
2The nano-pipe array thin film sample; Short TiO with gained
2Nano-pipe array thin film samples with water flushing is placed in the baking oven dry, be cooled to room temperature after, again through sintering, obtain short TiO
2Nano-tube array film electrode;
2) with the short TiO behind the sintering
2Nano-tube array film electrode is a working electrode, is reference electrode with Ag-AgCl, is counter electrode with Pt, the metabisulfite solution that adds volumetric molar concentration and be 0.01-1M in organic pollutant solution is as ionogen, and apply bias-voltage 0.4-1.2V, and open light source, organic pollutant is degraded.
2. according to the short TiO of the utilization of claim 1
2The method of nano-tube array film electrode photoelectric catalysis degrading organic, the electrolyte solution that it is characterized in that described fluoride ion is a hydrofluoric acid aqueous solution, and wherein the mass percent of fluorion is 0.2-1%, and the compound that constitutes fluorion is a hydrofluoric acid.
3. according to the short TiO of the utilization of claim 1
2The method of nano-tube array film electrode photoelectric catalysis degrading organic is characterized in that described short TiO
2During nano-pipe array thin film sample sintering, its sintering temperature is 400～700 ℃, and sintering time is 0.5-3 hour, and sintering atmosphere is air atmosphere or oxygen atmosphere.
4. according to the short TiO of the utilization of claim 1
2The method of nano-tube array film electrode photoelectric catalysis degrading organic is characterized in that described short TiO
2Nano-tube array film electrode, its pipe range scope is 70-300nm.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798126A (en) * | 2010-04-23 | 2010-08-11 | 四川大学 | Method for treating industrial waste water by means of photoelectrocatalysis |
| CN102942277A (en) * | 2012-11-14 | 2013-02-27 | 东南大学 | Method for enhancing photoelectric catalytic degradation effect of tetracycline drugs |
| CN103285843B (en) * | 2013-06-06 | 2015-04-22 | 重庆三峡学院 | TiO2 nano particle/TiO2 nanotube array and application thereof |
| CN104909437B (en) * | 2015-06-25 | 2017-04-12 | 清华大学 | Method for efficiently removing nitrate from water by Ti nano-electrode |
| CN108911056B (en) * | 2018-03-23 | 2021-06-04 | 同济大学 | Preparation and application of {001} crystal face controllable exposure titanium dioxide photoelectrode |
| CN111359677B (en) * | 2020-03-13 | 2023-03-28 | 湖北文理学院 | Preparation method of photoelectric catalyst for selectively degrading dibutyl phthalate |
| CN113189174B (en) * | 2021-02-09 | 2023-08-04 | 同济大学 | Titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property and preparation and application thereof |
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