CN103964563B - A kind of efficient degradation organic visible ray photoelectricity-Fenton method - Google Patents
A kind of efficient degradation organic visible ray photoelectricity-Fenton method Download PDFInfo
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Abstract
The invention discloses a kind of efficient degradation organic visible ray photoelectricity-Fenton method, collect visible ray, TiO2Photocatalysis and electricity-Fenton are in one, and Organic substance is degraded by composition visible ray photoelectricity-Fenton system, and concrete operation step is: preparation TNTs electrode and Fe2O3/ TNTs electrode; With TNTs electrode or Fe2O3/ TNTs electrode is anode, graphite or NACF is negative electrode, forms visible ray photoelectricity-Fenton system, Organic substance is degraded. The present invention is by TiO2Photocatalysis, electrochemical oxidation and Fenton oxidation technology combine, and introduce visible ray, form visible ray photoelectricity-Fenton system, by homemade TNTs electrode and Fe2O3/ TNTs electrode is in visible ray photoelectricity-Fenton system, it is achieved under visible light Organic substance is carried out efficient degradation.
Description
Technical field
The invention belongs to environmental protection and treatment field, be specifically related to a kind of efficient degradation organic visible ray photoelectricity-Fenton method.
Background technology
Photocatalysis technology is a kind of effective way of degraded environmental contaminants, is widely used in environment organic degraded. In photocatalysis technology, TiO2Photocatalysis is extensively had deep love for by scholar by its good stability, the advantage such as pollution-free, nontoxic. But traditional powder TiO2Photocatalysis technology still faces visible ray without problems such as response, the separation of catalyst difficulty, the easy compounds in electron hole, limits its further application in the depollution of environment. The proposition of photoelectric technology well solve catalyst fix, the problem of the separation of electron hole, be subject to the favor of vast researcher. It is based especially on TiO2The photo-electrocatalytic technology of nanotube electrode, has been demonstrated have certain visible light catalytic performance.
Although TiO2Nanotube electrode photo-electrocatalytic technology compensate for the deficiency of traditional photocatalysis technology, but the low problem of photocatalysis efficiency remains without and effectively solved, and limits its further popularization and application. For solving TiO2The combination technology of the problem that nanotube electrode photocatalysis efficiency is low, photocatalysis technology and high-level oxidation technology arises at the historic moment. Electricity-Fenton technology is a kind of efficient processing method in high-level oxidation technology, and OH, the OH that can produce oxidisability extremely strong by Fenton reaction contact with pollutant, are directly oxidized into H2O��CO2And small organic molecule, the removal efficiency of pollutant is higher. But the consumption of electric energy is relatively big, limit its application to a certain extent. Etc. KhataeeA.R. point out: if by TiO2Nanotube electrode photocatalysis technology is combined with electricity-Fenton technology, not only can solve the problem that photocatalysis efficiency is low, also solves the problem that electricity-Fenton process energy consumption is big to a certain extent. To TiO2The research that nanotube electrode photocatalysis technology is combined with electricity-Fenton technology focuses mostly at ultraviolet light, ultraviolet light only accounts for a little part in sunlight, if visible light application can be had certain effect in photoelectricity-Fenton reaction system the removal to pollutant, will to utilizing solar energy to process waste water generation inspiration.
Therefore, the TiO that under visible ray, photoelectrocatalysis efficiency is high is prepared2Nanotube electrode, and to its carry out visible ray modifiy, to improve its response under visible light further, improve the visible ray photoelectricity-Fenton system degradation capability to pollutant, there is positive meaning.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of efficient degradation organic visible ray photoelectricity-Fenton method that can improve photocatalysis efficiency, the processing cost of reduction electricity-Fenton, raising visible ray utilization rate.
The present invention is achieved by the following technical solutions:
A kind of efficient degradation organic visible ray photoelectricity-Fenton method, collects visible ray, TiO2Photocatalysis and electricity-Fenton, in one, form visible ray photoelectricity-Fenton system, Organic substance are carried out efficient degradation, and its concrete operation step is as follows:
(1) anodizing prepares TiO2Nanotube electrode, i.e. TNTs electrode:
Ti substrate material is sequentially carried out polishing, chemical polishing, ultrasonic waves for cleaning process, and then using the Ti substrate material after process as anode, graphite electrode is as negative electrode, with containing NH4F be the glycerol mixed solution of 0.1��0.5wt% concentration as electrolyte, the volume ratio of glycerol and water is 4:1��9:1, adopts the unidirectional current of 10��30V to carry out electrochemical anodic oxidation process, obtains unformed TNTs electrode after 30��90min; 500��600 DEG C of calcining at constant temperature 60��150min in tube type resistance furnace, obtain the TNTs electrode with crystal formation, standby;
(2) cathode electrodeposition prepares Fe2O3Modified TiO2Nanotube electrode, i.e. Fe2O3/ TNTs electrode:
The TNTs electrode with crystal formation step (1) prepared is immersed in the ferric salt solution that concentration is 0.025��0.25mmol/L ultrasonic, it is then transferred in the sulfate liquor that concentration is 0.05��0.2mmol/L, with graphite for anode, TNTs electrode is negative electrode, keep constant voltage 5��15V, carry out electro-deposition, make Fe3+Uniform deposition, in the pore of TNTs electrode, namely obtains Fe/TNTs electrode. Again using Fe/TNTs electrode as anode, inert electrode is negative electrode, and in the alkaline electrolyte that concentration is 0.5��2mol/L, constant voltage carries out anodic oxidation, makes Fe/TNTs electrode be transformed into corresponding Fe2O3/ TNTs electrode;
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The Fe that the TNTs electrode obtain step (1) or step (2) obtain2O3/ TNTs electrode is as anode, and negative electrode, as negative electrode, is carried out aeration by aerator by carbonaceous material, applies DC voltage-stabilizing and 150W xenon lamp visible light exposure simultaneously, forms visible ray photoelectricity-Fenton system; Utilize visible ray photoelectricity-Fenton system that organic pollution is degraded.
In described step (1), the crystal formation of TNTs electrode is the mixing crystal formation of anatase and rutile.
In described step (2), trivalent iron salt is Fe (NO3)3��9H2O��Fe2(SO4)3��9H2O��FeCl3��6H2One in O; Sulfate is Na2SO4Or K2SO4��
In described step (2), ultrasonic time is 5��20min, electrodeposition time 10��30min.
In described step (2), inert electrode is Pt electrode or graphite electrode, and alkaline solution is KOH or NaOH, anodizing time 1��5min.
In described step (3), carbonaceous material is graphite or NACF, and the plate spacing between anode and negative electrode is 2��6cm, and control anode voltage is 5��30V.
In described step (3), aeration control aeration rate is 0.5��2.5L/min, it is seen that the pH of light photoelectricity-Fenton system is 2��5, and support electrolyte is NaNO3Or Na2SO4, concentration is 1��10g/L, Fe2+Dosage be 0.1��1.5mmol/L.
The present invention is as follows relative to the advantage of prior art and good effect:
1, the present invention adopts anodizing to prepare TNTs electrode on Ti substrate material, can prepare the TNTs of regular appearance, size uniformity, and easy and simple to handle, condition is easily-controllable; Traditional powder body TiO is replaced with TNTs2, the vertical stratification of TNTs electrode, transmission and diffusion for electronics provide more convenient passage, decrease the compound of photo-generate electron-hole, also solve powder body TiO simultaneously2The catalyst difficulty existed separates, easily causes secondary pollution problems.
2, TNTs electrode photocatalysis is combined by the present invention with electricity-Fenton technology, and two systems combine, synergism, substantially increases the degradation capability to organic pollution, forms combination technique theoretical, provides new approach for organic degraded.
3, the TNTs electrode of preparation is modified by the present invention, prepares Fe2O3/ TNTs electrode, increases its response under visible light, improves it under visible light to organic degradation capability.
4, present invention introduces visible ray, it is to avoid using the potential safety hazard existed during ultraviolet light, required cost also reduces accordingly, meanwhile, this system to utilizing solar energy to have positive guiding function, has certain commercial introduction and is worth.
Accompanying drawing explanation
FE-SEM figure, Fig. 1 b that Fig. 1 a is the TNTs electrode prepared under experiment condition in example 2 are the Fe prepared under experiment condition in example 22O3The FE-SEM figure of/TNTs electrode.
Fig. 2 is the XRD figure prepared under experiment condition in example 2, and wherein, curve a is the XRD figure of TNTs electrode, and curve b is Fe2O3The XRD figure of/TNTs electrode.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
(1) anodizing prepares TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopts acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively. Using the Ti substrate material after process as anode, graphite electrode is 4cm as the plate spacing of negative electrode, anode and negative electrode, uses NH4F and glycerol mixed solution are as electrolyte, and the volume ratio of glycerol and water is 9:1, containing NH4The concentration of F is 0.5wt%. Make wire with copper wire and two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction. Controlling voltage in the reaction is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Being 20 DEG C/min then through programming rate, calcining heat is in the tube type resistance furnace of 600 DEG C after high-temperature calcination 120min, obtains the TNTs electrode with certain crystal formation.
(2) form visible ray photoelectricity-Fenton system and Organic substance degraded:
TNTs electrode step (1) obtained respectively is as anode, and graphite electrode material is negative electrode, with rectangle PVC groove for cell reaction groove. The plate spacing of anode and negative electrode is 5cm, the anode voltage controlled is 20V, by aerator, negative electrode is carried out aeration, and control aeration rate is 1.5L/min, applying visible light exposure is 150W xenon lamp, composition visible ray photoelectricity-Fenton system (TNTs+ graphite+illumination).
Using the RhB of 20mg/L as needs degradable organic pollutant, putting in visible ray photoelectricity-Fenton system and carry out degradation reaction, remain and at the uniform velocity stir in course of reaction, in this system, reaction solution pH is 3, and support electrolyte is Na2SO4Dosage be 10g/L;Fe2+Dosage be 1mmol/L. respectively by visible light photocatalysis system (TNTs+ light source), electricity-Fenton system (TNTs+ graphite), RhB is degraded by visible ray photoelectricity-Fenton system (TNTs+ graphite+light source), course of reaction remains and at the uniform velocity stirs, the clearance of RhB is respectively 4.12% by 60min, 44.26%, 68.52%, TNTs photocatalysis is combined with electricity-Fenton technology, in composition visible ray photoelectricity-Fenton system, treatment effect significantly improves, and clearance adding and big 20.14% than independent photocatalysis and electricity-Fenton clearance, show that two systems exist synergism.
Embodiment 2:
(1) anodizing prepares TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopts acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively. Using the Ti substrate material after process as anode, graphite electrode is 4cm as the plate spacing of negative electrode, anode and negative electrode, uses NH4F and glycerol mixed solution are as electrolyte, and the volume ratio of glycerol and water is 9:1, containing NH4The concentration of F is 0.5wt%. Make wire with copper wire and two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction. Controlling voltage in the reaction is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Being 20 DEG C/min then through programming rate, calcining heat is in the tube type resistance furnace of 600 DEG C after high-temperature calcination 120min, obtains the TNTs electrode with certain crystal formation.
(2) cathode electrodeposition prepares Fe2O3/ TNTs electrode:
The TNTs electrode (1) prepared is immersed in the Fe (NO of 0.05mol/L3)3��9H2In O solution, carry out supersound process 10min, be then transferred into the Na of 0.1mol/L2SO4In solution, with graphite be anode, TNTs electrode for negative electrode, keep 8V constant voltage, electro-deposition 20min, make Fe3+Uniform deposition, in the pore of TNTs, namely obtains Fe/TNTs electrode. Again using Fe/TNTs electrode as anode, graphite electrode is negative electrode, in the KOH electrolyte of 1mol/L, adopts the constant voltage of 8V to carry out anodic oxidation 2min, obtains Fe2O3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The TNTs electrode respectively step (1), (2) obtained or Fe2O3/ TNTs electrode is as anode, and graphite electrode material is negative electrode, with rectangle PVC groove for cell reaction groove. The plate spacing of anode and negative electrode is 5cm, the anode voltage controlled is 20V, by aerator, negative electrode is carried out aeration, and control aeration rate is 1.5L/min, applying visible light exposure is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (TNTs+ graphite+light source, Fe2O3/ TNTs+ graphite+light source). By this visible ray photoelectricity-Fenton system, organic pollution is degraded.
Using the RhB of 20mg/L as needs degradable organic pollutant, putting in visible ray photoelectricity-Fenton system and carry out degradation reaction, remain and at the uniform velocity stir in course of reaction, in this system, reaction solution pH is 3, and support electrolyte is Na2SO4Dosage be 10g/L; Fe2+Dosage be 1mmol/L. Respectively by visible ray photoelectro-Fenton process system (TNTs+ graphite+light source), it is seen that light photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source) RhB is degraded, course of reaction remains and at the uniform velocity stirs, the clearance of RhB is respectively 69.15%, 77.29% by 60min, after TNTs electrode is modified, the Fe prepared2O3/ TNTs electrode is in visible ray photoelectricity-Fenton system, and treatment effect has the raising of 8.14% compared with TNTs.
Embodiment 3:
(1) anodizing prepares TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopts acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively. Using the Ti substrate material after process as anode, graphite electrode is 4cm as the plate spacing of negative electrode, anode and negative electrode, uses NH4F and glycerol mixed solution are as electrolyte, and the volume ratio of glycerol and water is 9:1, containing NH4The concentration of F is 0.5wt%. Make wire with copper wire and two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction. Controlling voltage in the reaction is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Being 20 DEG C/min then through programming rate, calcining heat is in the tube type resistance furnace of 600 DEG C after high-temperature calcination 120min, obtains the TNTs electrode with certain crystal formation.
(2) cathode electrodeposition prepares Fe2O3/ TNTs electrode:
The TNTs electrode (1) prepared is immersed in the Fe of 0.025mol/L2(SO4)3��9H2In O solution, carry out supersound process 15min, be then transferred into the Na of 0.1mol/L2SO4In solution, with graphite be anode, TNTs electrode for negative electrode, keep 10V constant voltage, electro-deposition 15min, make Fe3+Uniform deposition, in the pore of TNTs, namely obtains Fe/TNTs electrode. Again using Fe/TNTs electrode as anode, graphite electrode is negative electrode, in the KOH electrolyte of 1mol/L, adopts the constant voltage of 10V to carry out anodic oxidation 3min, obtains Fe2O3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The Fe that step (2) is obtained2O3/ TNTs electrode is as anode, respectively using graphite or NACF (hereinafter referred to as ACF) electrode as negative electrode, with rectangle PVC groove for cell reaction groove. The plate spacing of anode and negative electrode is 4cm, and the anode voltage of control is 15V, by aerator, negative electrode is carried out aeration, and control aeration rate is 1.0L/min, and applying visible light exposure is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source, Fe2O3/ TNTs+ACF+ light source). By visible ray photoelectricity-Fenton system, organic pollution is degraded.
Using the RhB of 10mg/L as needs degradable organic pollutant, putting in visible ray photoelectricity-Fenton system and carry out degradation reaction, remain and at the uniform velocity stir in course of reaction, in this system, reaction solution pH is 3, and support electrolyte is Na2SO4Dosage be 10g/L; Fe2+Dosage be 1mmol/L. Respectively with visible ray photoelectro-Fenton process system (Fe2O3/ TNTs+ graphite+light source), it is seen that light photoelectricity-Fenton system (Fe2O3/ TNTs+ACF+ light source) RhB is degraded, course of reaction remains and at the uniform velocity stirs, the clearance of RhB is respectively 74.15%, 81.33% by 60min, with the Fe of preparation2O3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material is become ACF from graphite, and treatment effect has the raising of 7.18%.
Embodiment 4:
(1) anodizing prepares TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopts acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively.Using the Ti substrate material after process as anode, graphite electrode is 4cm as the plate spacing of negative electrode, anode and negative electrode, uses NH4F and glycerol mixed solution are as electrolyte, and the volume ratio of glycerol and water is 9:1, containing NH4The concentration of F is 0.5wt%. Make wire with copper wire and two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction. Controlling voltage in the reaction is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Being 20 DEG C/min then through programming rate, calcining heat is in the tube type resistance furnace of 600 DEG C after high-temperature calcination 120min, obtains the TNTs electrode with certain crystal formation.
(2) cathode electrodeposition prepares Fe2O3/ TNTs electrode:
The TNTs electrode (1) prepared is immersed in the FeCl of 0.05mol/L3��6H2In O solution, carry out supersound process 10min, be then transferred into the K of 0.1mol/L2SO4In solution, with graphite be anode, TNTs electrode for negative electrode, keep 5V constant voltage, electro-deposition 30min, make Fe3+Uniform deposition, in the pore of TNTs, namely obtains Fe/TNTs electrode. Again using Fe/TNTs electrode as anode, graphite electrode is negative electrode, in the NaOH electrolyte of 1mol/L, adopts the constant voltage of 5V to carry out anodic oxidation 5min, obtains Fe2O3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The TNTs electrode respectively step (1), (2) obtained or Fe2O3/ TNTs electrode is as anode, and graphite electrode material is negative electrode, with rectangle PVC groove for cell reaction groove. The plate spacing of anode and negative electrode is 6cm, the anode voltage controlled is 30V, by aerator, negative electrode is carried out aeration, and control aeration rate is 1.5L/min, applying visible light exposure is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (TNTs+ graphite+light source, Fe2O3/ TNTs+ graphite+light source). By visible ray photoelectricity-Fenton system, organic pollution is degraded.
Using the RhB of 30mg/L as needs degradable organic pollutant, putting in visible ray photoelectricity-Fenton system and carry out degradation reaction, remain and at the uniform velocity stir in course of reaction, in this system, reaction solution pH is 3, and support electrolyte is Na2SO4Dosage be 5g/L; Fe2+Dosage be 1mmol/L. Respectively by visible ray photoelectro-Fenton process system (TNTs+ graphite+light source), it is seen that light photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source) RhB is degraded, course of reaction remains and at the uniform velocity stirs, the clearance of RhB is respectively 61.68%, 67.69% by 60min, after TNTs electrode is modified, the Fe prepared2O3/ TNTs electrode is in visible ray photoelectricity-Fenton system, and treatment effect has the raising of 6.01% compared with TNTs.
Embodiment 5:
(1) anodizing prepares TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopts acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively. Using the Ti substrate material after process as anode, graphite electrode is 4cm as the plate spacing of negative electrode, anode and negative electrode, uses NH4F and glycerol mixed solution are as electrolyte, and the volume ratio of glycerol and water is 9:1, containing NH4The concentration of F is 0.5wt%. Make wire with copper wire and two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction. Controlling voltage in the reaction is 20V, and anodizing time is 90min, obtains unformed TNTs electrode;Being 20 DEG C/min then through programming rate, calcining heat is in the tube type resistance furnace of 600 DEG C after high-temperature calcination 120min, obtains the TNTs electrode with certain crystal formation.
(2) cathode electrodeposition prepares Fe2O3/ TNTs electrode:
The TNTs electrode (1) prepared is immersed in the Fe of 0.025mol/L2(SO4)3��9H2In O solution, carry out supersound process 10min, be then transferred into the Na of 0.2mol/L2SO4In solution, with graphite be anode, TNTs electrode for negative electrode, keep 5V constant voltage, electro-deposition 15min, make Fe3+Uniform deposition, in the pore of TNTs, namely obtains Fe/TNTs electrode. Again using Fe/TNTs electrode as anode, graphite electrode is negative electrode, in the KOH electrolyte of 1mol/L, adopts the constant voltage of 5V to carry out anodic oxidation 5min, obtains Fe2O3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The Fe respectively step (2) obtained2O3/ TNTs electrode is negative electrode as anode, graphite or NACF (ACF) electrode, with rectangle PVC groove for cell reaction groove. The plate spacing of anode and negative electrode is 4cm, and the anode voltage of control is 30V, by aerator, negative electrode is carried out aeration, and control aeration rate is 1.5L/min, and applying visible light exposure is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source, Fe2O3/ TNTs+ACF+ light source). By visible ray photoelectricity-Fenton system, organic pollution is degraded.
Using the RhB of 40mg/L as needs degradable organic pollutant, putting in visible ray photoelectricity-Fenton system and carry out degradation reaction, remain and at the uniform velocity stir in course of reaction, in this system, reaction solution pH is 3, and support electrolyte is Na2SO4Dosage be 5g/L; Fe2+Dosage be 1.5mmol/L. Respectively with visible ray photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source), it is seen that light photoelectricity-Fenton system (Fe2O3/ TNTs+ACF+ light source) RhB is degraded, course of reaction remains and at the uniform velocity stirs, the clearance of RhB is respectively 65.58%, 71.18% by 60min, with the Fe of preparation2O3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material is become ACF from graphite, and treatment effect has the raising of 5.60%.
Embodiment 6:
(1) anodizing prepares TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopts acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively. Using the Ti substrate material after process as anode, graphite electrode is 4cm as the plate spacing of negative electrode, anode and negative electrode, uses NH4F and glycerol mixed solution are as electrolyte, and the volume ratio of glycerol and water is 9:1, containing NH4The concentration of F is 0.5wt%. Make wire with copper wire and two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction. Controlling voltage in the reaction is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Being 20 DEG C/min then through programming rate, calcining heat is in the tube type resistance furnace of 500 DEG C after high-temperature calcination 150min, obtains the TNTs electrode with certain crystal formation.
(2) cathode electrodeposition prepares Fe2O3/ TNTs electrode:
The TNTs electrode (1) prepared is immersed in the Fe of 0.25mol/L2(SO4)3��9H2In O solution, carry out supersound process 5min, be then transferred into the Na of 0.05mol/L2SO4In solution, with Pt be anode, TNTs electrode for negative electrode, keep 15V constant voltage, electro-deposition 10min, make Fe3+Uniform deposition, in the pore of TNTs, namely obtains Fe/TNTs electrode.Again using Fe/TNTs electrode as anode, graphite electrode is negative electrode, in the KOH electrolyte of 0.5mol/L, adopts the constant voltage of 15V to carry out anodic oxidation 1min, obtains Fe2O3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The Fe respectively step (2) obtained2O3/ TNTs electrode is negative electrode as anode, graphite and NACF (ACF) electrode, with rectangle PVC groove for cell reaction groove. The plate spacing of anode and negative electrode is 2cm, and the anode voltage of control is 5V, by aerator, negative electrode is carried out aeration, and control aeration rate is 0.5L/min, and applying visible light exposure is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source, Fe2O3/ TNTs+ACF+ light source). By visible ray photoelectricity-Fenton system, organic pollution is degraded.
Using the RhB of 40mg/L as needs degradable organic pollutant, putting in visible ray photoelectricity-Fenton system and carry out degradation reaction, remain and at the uniform velocity stir in course of reaction, in this system, reaction solution pH is 3, and support electrolyte is NaNO3Dosage be 5g/L; Fe2+Dosage be 0.1mmol/L. Respectively with visible ray photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source), it is seen that light photoelectricity-Fenton system (Fe2O3/ TNTs+ACF+ light source) RhB is degraded, course of reaction remains and at the uniform velocity stirs, the clearance of RhB is respectively 41.17%, 46.66% by 60min, with the Fe of preparation2O3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material is become ACF from graphite, and treatment effect has the raising of 5.49%.
Embodiment 7:
(1) anodizing prepares TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopts acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively. Using the Ti substrate material after process as anode, graphite electrode is 4cm as the plate spacing of negative electrode, anode and negative electrode, uses NH4F and glycerol mixed solution are as electrolyte, and the volume ratio of glycerol and water is 4:1, containing NH4The concentration of F is 0.1wt%. Make wire with copper wire and two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction. Controlling voltage in the reaction is 20V, and anodizing time is 30min, obtains unformed TNTs electrode; Being 20 DEG C/min then through programming rate, calcining heat is in the tube type resistance furnace of 600 DEG C after high-temperature calcination 60min, obtains the TNTs electrode with certain crystal formation.
(2) cathode electrodeposition prepares Fe2O3/ TNTs electrode:
The TNTs electrode (1) prepared is immersed in the Fe of 0.25mol/L2(SO4)3��9H2In O solution, carry out supersound process 20min, be then transferred into the Na of 0.15mol/L2SO4In solution, with Pt be anode, TNTs electrode for negative electrode, keep 10V constant voltage, electro-deposition 10min, make Fe3+Uniform deposition, in the pore of TNTs, namely obtains Fe/TNTs electrode. Again using Fe/TNTs electrode as anode, Pt electrode is negative electrode, in the KOH electrolyte of 2mol/L, adopts the constant voltage of 10V to carry out anodic oxidation 2min, obtains Fe2O3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The Fe respectively step (2) obtained2O3/ TNTs electrode is negative electrode as anode, graphite and NACF (ACF) electrode, with rectangle PVC groove for cell reaction groove.The plate spacing of anode and negative electrode is 6cm, and the anode voltage of control is 10V, by aerator, negative electrode is carried out aeration, and control aeration rate is 2.5L/min, and applying visible light exposure is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe2O3/ TNTs+ graphite+light source, Fe2O3/ TNTs+ACF+ light source). By visible ray photoelectricity-Fenton system, organic pollution is degraded.
Using the RhB of 40mg/L as needs degradable organic pollutant, putting in visible ray photoelectricity-Fenton system and carry out degradation reaction, remain and at the uniform velocity stir in course of reaction, in this system, reaction solution pH is 5, and support electrolyte is NaNO3Dosage be 5g/L; Fe2+Dosage be 1.5mmol/L. Respectively with visible ray photoelectro-Fenton process system (Fe2O3/ TNTs+ graphite+light source), it is seen that light photoelectricity-Fenton system (Fe2O3/ TNTs+ACF+ light source) RhB is degraded, course of reaction remains and at the uniform velocity stirs, the clearance of RhB is respectively 42.22%, 48.66% by 60min, with the Fe of preparation2O3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material is become ACF from graphite, and treatment effect has the raising of 6.44%.
Claims (3)
1. an efficient degradation organic visible ray photoelectricity-Fenton method, it is characterised in that collection visible ray, TiO2Photocatalysis and electricity-Fenton, in one, form visible ray photoelectricity-Fenton system, Organic substance are carried out efficient degradation, and its concrete operation step is as follows:
(1) anodizing prepares TiO2Nanotube electrode, i.e. TNTs electrode:
By purity > abrasive paper for metallograph of Ti substrate material 500#, 1000#, 1500# of 99.6% is sequentially carried out polishing, until smooth surface, then to immerse volume ratio be HF:HNO3: H2The polishing fluid of O=1:4:5 carries out chemical polishing 30s, then adopting acetone, ethanol, pure water to be placed in ultrasonic cleaner cleaning treatment successively, using the Ti substrate material after processing as anode, graphite electrode is as negative electrode, the plate spacing of anode and negative electrode is 4cm, with containing NH4The glycerol mixed solution of F is as electrolyte, and in described electrolyte, glycerol is 9:1 or 4:1 with the volume ratio of water, when the volume ratio of glycerol Yu water is 9:1, and NH4F concentration in the electrolytic solution is 0.5wt%; When the volume ratio of glycerol Yu water is 4:1, NH4F concentration in the electrolytic solution is 0.1wt%; The unidirectional current adopting 10��30V carries out electrochemical anodic oxidation process, obtains unformed TNTs electrode after 30��90min; Then through calcining at constant temperature 60��150min in programming rate to be 20 DEG C/min, calcining heat the be tube type resistance furnace of 500��600 DEG C, obtain the TNTs electrode with the mixing crystal formation of anatase and rutile, standby;
(2) cathode electrodeposition prepares Fe2O3Modified TiO2Nanotube electrode, i.e. Fe2O3/ TNTs electrode:
The TNTs electrode with crystal formation step (1) prepared is immersed in the ferric salt solution that concentration is 0.025��0.25mmol/L ultrasonic, it is then transferred in the sulfate liquor that concentration is 0.05��0.2mmol/L, with graphite for anode, TNTs electrode is negative electrode, keep constant voltage 5��15V, carry out electro-deposition, make Fe3+Uniform deposition, in the pore of TNTs electrode, namely obtains Fe/TNTs electrode; Again using Fe/TNTs electrode as anode, inert electrode is negative electrode, and in the alkaline electrolyte that concentration is 0.5��2mol/L, constant voltage carries out anodic oxidation, and anodizing time is 1-5min, makes Fe/TNTs electrode be transformed into corresponding Fe2O3/ TNTs electrode;
Ultrasonic time is 5��20min, electrodeposition time 10��30min;
(3) form visible ray photoelectricity-Fenton system and Organic substance degraded:
The Fe that the TNTs electrode obtain step (1) or step (2) obtain2O3/ TNTs electrode is as anode, graphite or NACF are as negative electrode, plate spacing between anode and negative electrode is 2��6cm, control anode voltage is 5��30V, by aerator, negative electrode is carried out aeration, and aeration control aeration rate is 0.5��2.5L/min, apply DC voltage-stabilizing and 150W xenon lamp visible light exposure simultaneously, composition visible ray photoelectricity-Fenton system, it is seen that the pH of light photoelectricity-Fenton system is 2��5, and support electrolyte is NaNO3Or Na2SO4, concentration is 1��10g/L, Fe2+Dosage be 0.1��1.5mmol/L; Utilize visible ray photoelectricity-Fenton system that organic pollution is degraded.
2. efficient degradation according to claim 1 organic visible ray photoelectricity-Fenton method, it is characterised in that in described step (2), trivalent iron salt is Fe (NO3)3��9H2O��Fe2(SO4)3��9H2O or FeCl3��6H2One in O; Sulfate is Na2SO4Or K2SO4��
3. efficient degradation according to claim 1 organic visible ray photoelectricity-Fenton method, it is characterized in that, in described step (2), inert electrode is Pt electrode or graphite electrode, alkaline solution is KOH or NaOH, anodizing time 1��5min.
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