CN103446699A - Method for cooperatively degrading organic matters by visible light photoelectric-Fenton - Google Patents
Method for cooperatively degrading organic matters by visible light photoelectric-Fenton Download PDFInfo
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- CN103446699A CN103446699A CN201310403332XA CN201310403332A CN103446699A CN 103446699 A CN103446699 A CN 103446699A CN 201310403332X A CN201310403332X A CN 201310403332XA CN 201310403332 A CN201310403332 A CN 201310403332A CN 103446699 A CN103446699 A CN 103446699A
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Abstract
The invention discloses a method for cooperatively degrading organic matters by visible light photoelectric-Fenton. According to the method, a visible light photoelectric-Fenton system formed by visible light, photocatalysis and electric-Fenton is used and the organic matters are put into the system to be degraded. The method comprises the specific steps of (1) preparing a mesoporous TiO2 thin film electrode; (2) forming the visible light photoelectric-Fenton system; and (3) degrading the organic matters. According to the method, a photocatalysis technology, a photoelectric oxidization technology and a Fenton oxidization technology are combined and the visible light is introduced to form the visible light photoelectric-Fenton system; the self-made mesoporous TiO2 thin film electrode is used in the visible light photoelectric-Fenton system to realize the mutual cooperative effect of the photocatalysis and the electric-Fenton under the visible light, so that the treatment effect on organic pollutants by the whole system is improved.
Description
Technical field
The invention belongs to environmental protection and improvement field, relate to a kind of method with visible ray photoelectricity-Fenton system degradation of organic substances.
Background technology
Photocatalysis has been widely used in environment in organic degraded, nano-TiO
2photochemical catalyst relies on the advantages such as catalytic performance is good, nontoxic, inexpensive, and the parent who is subject to researchers looks at.Conventional Ti O
2photochemical catalyst is the powder form, exists the catalyst difficulty to separate, easily cause secondary pollution problems.Mesoporous TiO
2, owing to thering is high specific area, orderly pore passage structure, aperture size is controlled, and surface is easy to the advantages such as modification, can solve conventional Ti O
2secondary pollution problems is separated, easily caused to the catalyst difficulty that photocatalysis exists.
Patent 200910306567.0 discloses preparation method and the application thereof of zinc ferrite/titanium dioxide nano compounded visible light photocatalyst, belongs to the environmental pollution treatment technology field.The catalyst preparation comprises the following steps: electrochemical oxidation reactions occurs under the hydrofluoric acid effect that (1) is 0.2wt% in concentration prepare titanium dioxide nanotube electrode, and the about 80nm of its nanotube caliber left and right, pipe range is 550mm; (2) adopt new electrodeposition process to prepare zinc ferrite/titanium dioxide nano compounded visible light photocatalyst.The method makes synthetic ZnFe
2o
4nanotube inside, thus the surface of particle packing at nanotube reduced, further improved the electronics transmission efficiency.In addition, being compounded in of zinc ferrite reduced light induced electron-hole shortcoming high to recombination probability to a certain extent, but also widened the photoresponse scope of titanium dioxide nanotube electrode, improved its photocatalytic degradation efficiency to organic pollution in visible-range.Yet the problem that photocatalysis efficiency is low still is not resolved, there is the scholar to begin one's study photocatalysis is combined with other high-level oxidation technologies, improve photocatalysis efficiency by coordinative role.Wherein, the photocatalysis composition photoelectricity-Fenton system that combines with electricity-Fenton technology, by this system, pollutant being processed is a kind of emerging technology, in the visual field that progresses in recent years people.The proposition of photoelectricity-Fenton system has improved light-catalysed efficiency, and whole system also is improved to the removal ability of pollutant, two systems is processed to organic pollution in conjunction with mutually acting synergistically simultaneously.
Patent 201010107539.9 discloses a kind of process of processing hardly-biodegradable organic wastewater, the method is mainly to utilize ultraviolet light, electrochemistry, the ultrasonic redox chemistry reacting phase that involves is in conjunction with being processed organic wastewater with difficult degradation thereby, waste water was entered to the ultrasonic cavitation district, 3 reaction members of electrochemical reaction district and ultraviolet catalytic reaction zone are processed, can realize ultrasonic processing method for waste water, ultraviolet cooperating Fenton reagent oxidation is processed waste water and electrochemistry and collaborative Fenton reagent oxidation thereof and is processed the high-efficiency multi-stage advanced wastewater oxidation reaction that method for waste water is tied mutually, can effectively process the organic wastewater of multiple hardly-biodegradable.But the method still only limits to the utilization of ultraviolet light, higher, the easy seldom part that human body is damaged, only accounts for sunshine of cost that ultraviolet light is required, these inevitable inferior positions can hinder further applying of the method.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of and can improve photocatalysis efficiency, reduced the method with visible ray photoelectricity-Fenton system degradation of organic substances of the processing cost of electricity-Fenton.
The present invention is achieved through the following technical solutions:
A kind of by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is the visible ray photoelectricity that utilizes visible ray, photocatalysis and electricity-Fenton to form-Fenton system, organic matter is placed in to this system and is degraded, and its concrete operation step is as follows:
(1) prepare mesoporous TiO
2membrane electrode: by the Ti substrate material polished successively, chemical polishing, Ultrasonic Cleaning process, then the Ti substrate material after processing is as anode, graphite or Pt electrode are as negative electrode, fluorine-containing inorganic aqueous solution or fluorine-containing organic solution are as electrolyte solution, after processing by electrochemistry anodic oxidation, obtain unformed mesoporous TiO
2membrane electrode; After high-temperature calcination in tube type resistance furnace, obtain having the mesoporous TiO of certain crystal formation again
2membrane electrode, standby;
(2) form visible ray photoelectricity-Fenton system: the mesoporous TiO that step (1) is obtained
2membrane electrode is as anode, and carbonaceous material, as negative electrode, carries out aeration by the aerator target, applies DC voltage-stabilizing and visible ray irradiation simultaneously, forms visible ray photoelectricity-Fenton system;
(3) organic matter is degraded: the organic matter of difficult degradation is placed in to the visible ray photoelectricity that step (2) obtains-Fenton system and is degraded.
In above-described step (1), the abrasive paper for metallograph that the sand paper that described polishing adopts is 500#, 1000#, 1500#, polishing successively.
In above-described step (1), the polishing fluid that described chemical polishing adopts is HF: HNO by following raw material and volume ratio
3: H
2o=1: form at 4: 5.
In above-described step (1), described fluorine-containing inorganic aqueous solution is HF solution, and the mass concentration of HF is 0.2 ~ 0.5 wt%; Described fluorine-containing organic solution is NH
4the mixed liquor of F and glycerine, in fluorine-containing organic solution, the volume ratio of glycerine and water is 1: 9, contains NH
4the mass concentration of F is 0.2 ~ 0.5 wt%.
In above-described step (1), controlling voltage in described electrochemistry anodic oxidation is 10 ~ 40V, and the distance between plates of anode and negative electrode is 3 ~ 5cm, and anodizing time is 30 ~ 150min.
In above-described step (1), it is 20 ℃/min that described tube type resistance furnace is controlled programming rate, and calcining heat is 400 ~ 700 ℃, and calcination time is 60 ~ 180 min.
In above-described step (2), described carbonaceous material is graphite or NACF.。
In above-described step (2), described anode, the negative electrode distance between plates between them is 3 ~ 7cm, and the control anode voltage is 10 ~ 40V.
In above-described step (2), described aeration control aeration rate is 0.5 ~ 2 L/min; The pH of described visible ray photoelectricity-Fenton system is 2 ~ 4, and the support electrolyte is Na
2sO
4, dosage is 5 ~ 10 g/L; Fe
2+dosage be 0.1 ~ 1 mM.
In above-described step (2), described visible ray irradiation is external lighting type, and the employing light source is xenon source.
The present invention is as follows with respect to advantage and the good effect of prior art:
1, the present invention adopts anodizing to prepare mesoporous TiO on the Ti substrate material
2film, can prepare that pattern is regular, the mesoporous TiO of size homogeneous
2film, easy and simple to handle, condition is easily controlled; With mesoporous TiO
2film replaces traditional powder TiO
2, mesoporous TiO
2the vertical stratification of film, for transmission and the diffusion of electronics provides more convenient passage, reduced the compound of light induced electron-hole, also solved powder TiO simultaneously
2secondary pollution problems is separated, easily caused to the catalyst difficulty existed.
2, the present invention is by mesoporous TiO
2film light catalysis is combined with electricity-Fenton technology, and two systems combine, and synergy, improved the degradation capability to organic pollution greatly, not only improved photocatalysis efficiency, has also reduced to a certain extent the energy consumption of electricity-Fenton simultaneously.
3, the present invention introduces visible ray, the potential safety hazard existed while having avoided using ultraviolet light, and required cost is corresponding reduction also, and simultaneously, this system, to utilizing solar energy that positive guiding function is arranged, has certain industrial promotional value.
The accompanying drawing explanation
Fig. 1 is the mesoporous TiO made under experiment condition in example 1
2the FE-SEM figure of membrane electrode.
Fig. 2 is the mesoporous TiO made under experiment condition in example 1
2the XRD figure of membrane electrode
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and graphite electrode is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerine mixed solution are as electrolyte, and the volume ratio of glycerine and water is 1:9, contains NH
4the concentration of F is 0.5 wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 30 V, and anodizing time is 90 min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 600 ℃, after high-temperature calcination 120 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and graphite, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 5 cm, and the anode voltage of control is 30 V, by the aerator target, carries out aeration, and controlling aeration rate is 1.5 L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 3, the support electrolyte is Na
2sO
4dosage be 5 g/L; Fe
2+dosage be 1 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 2.78%, 30.87%, 69.92%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 108% than photocatalysis and Fenton system.
Embodiment 2:
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and graphite electrode is as negative electrode, and the distance between plates of anode and negative electrode is 5cm, uses NH
4f and glycerine mixed solution are as electrolyte, and the volume ratio of glycerine and water is 1:9, contains NH
4the concentration of F is 0.3wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 10 V, and anodizing time is 150 min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 400 ℃, after high-temperature calcination 180 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and NACF, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 3 cm, and controlling anode voltage is 10 V, by the aerator target, carries out aeration, and controlling aeration rate is 0.5 L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 4, the support electrolyte is Na
2sO
4dosage be 10 g/L; Fe
2+dosage be 0.1 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 2.71%, 39.89%, 65.72%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 54.3% than photocatalysis and Fenton system.
Embodiment 3:
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and graphite electrode is as negative electrode, and the distance between plates of anode and negative electrode is 3cm, uses NH
4f and glycerine mixed solution are as electrolyte, and the volume ratio of glycerine and water is 1:9, contains NH
4the concentration of F is 0.2wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 40 V, and anodizing time is 90 min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 500 ℃, after high-temperature calcination 120 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and graphite, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 4 cm, and controlling anode voltage is 40 V, by the aerator target, carries out aeration, and controlling aeration rate is 1 L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 2, the support electrolyte is Na
2sO
4dosage be 8 g/L; Fe
2+dosage be 0.5 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 2.91%, 33.74%, 69.52%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 89.69% than photocatalysis and Fenton system.
Embodiment 4:
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and graphite electrode is as negative electrode, and the distance between plates of anode and negative electrode is 3cm, uses NH
4f and glycerine mixed solution are as electrolyte, and the volume ratio of glycerine and water is 1:9, contains NH
4the concentration of F is 0.4wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 20 V, and anodizing time is 60 min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 700 ℃, after high-temperature calcination 60 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and graphite, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 7 cm, and controlling anode voltage is 20 V, by the aerator target, carries out aeration, and controlling aeration rate is 2 L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 3, the support electrolyte is Na
2sO
4dosage be 5 g/L; Fe
2+dosage be 1 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 5.43%, 30.31%, 67.35%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 88.4% than photocatalysis and Fenton system.
Embodiment 5:
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and the Pt electrode is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, with the HF aqueous solution, is electrolyte, and wherein HF is 0.4 wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 30 V, and anodizing time is 150 min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 600 ℃, after high-temperature calcination 120 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and graphite, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 5 cm, and controlling anode voltage is 30 V, by the aerator target, carries out aeration, and the control aeration rate is 1.5L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 3, the support electrolyte is Na
2sO
4dosage be 5 g/L; Fe
2+dosage be 1 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 4.56%, 37.87%, 67.16%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 58.3% than photocatalysis and Fenton system.
Embodiment 6:
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and graphite electrode is as negative electrode, and the distance between plates of anode and negative electrode is 5cm, with the HF aqueous solution, is electrolyte, and wherein HF is 0.5 wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 10 V, and anodizing time is 30min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 700 ℃, after high-temperature calcination 180 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and NACF, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 5 cm, and controlling anode voltage is 10 V, by the aerator target, carries out aeration, and controlling aeration rate is 0.5 L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 4, the support electrolyte is Na
2sO
4dosage be 10 g/L; Fe
2+dosage be 0.1 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 3.59%, 33.05%, 61.58%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 68.1% than photocatalysis and Fenton system.
Embodiment 7:
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and the Pt electrode is as negative electrode, and the distance between plates of anode and negative electrode is 3cm, with the HF aqueous solution, is electrolyte, and wherein HF is 0.3 wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 40 V, and anodizing time is 60min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 400 ℃, after high-temperature calcination 60 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and graphite, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 3 cm, and controlling anode voltage is 40 V, by the aerator target, carries out aeration, and controlling aeration rate is 2 L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 2, the support electrolyte is Na
2sO
4dosage be 8 g/L; Fe
2+dosage be 1 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 4.83%, 34.54%, 71.00%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 80.3% than photocatalysis and Fenton system.
Embodiment 8
By purity>abrasive paper for metallograph of Ti 500#, 1000#, the 1500# for substrate material of 99.6 % is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2carry out chemical polishing 30 s in the polishing fluid of O=1:4:5, then adopt successively acetone, pure water to be placed in the ultrasonic cleaning machine cleaning treatment.Ti substrate material after processing is as anode, and graphite electrode is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, with the HF aqueous solution, is electrolyte, and wherein HF is 0.2 wt%.Make wire with copper wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.Controlling voltage in this reaction is 30 V, and anodizing time is 90min, obtains unformed mesoporous TiO
2membrane electrode; Be 20 ℃/min through programming rate again, in the tube type resistance furnace that calcining heat is 600 ℃, after high-temperature calcination 120 min, obtain having the mesoporous TiO of certain crystal formation
2membrane electrode.
By the mesoporous TiO prepared
2membrane electrode is as anode, and NACF, as negative electrode, be take rectangle PVC groove as the cell reaction groove.The distance between plates of anode and negative electrode is 7 cm, and controlling anode voltage is 30 V, by the aerator target, carries out aeration, and controlling aeration rate is 1.5 L/min, and applying visible ray irradiation is 150 W xenon lamps, forms visible ray photoelectricity-Fenton system.
Using the rhodamine B of 20 mg/L as the needs degradable organic pollutant, carry out degradation reaction in the visible ray photoelectricity of putting into-Fenton system, remain in course of reaction at the uniform velocity and stir, in this system, reaction solution pH is 3, the support electrolyte is Na
2sO
4dosage be 5 g/L; Fe
2+dosage be 0.5 mM.Carry out respectively visible light photocatalysis (add illumination, no power, aeration, do not add Fe
2+,), Fenton (do not add illumination, the energising, aeration, add Fe
2+,), photoelectricity Fenton test (add illumination, energising, aeration, add Fe
2+,), remaining in course of reaction at the uniform velocity and to stir, 30min is to the clearance of rhodamine B for being respectively 3.23%, 36.33%, 63.24%, and the clearance of visible ray photoelectricity Fenton system adds and has improved 59.86% than photocatalysis and Fenton system.
Claims (10)
1. one kind by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: it is the visible ray photoelectricity that utilizes visible ray, photocatalysis and electricity-Fenton to form-Fenton system, organic matter is placed in to this system and is degraded, its concrete operation step is as follows:
(1) prepare mesoporous TiO
2membrane electrode: by the Ti substrate material polished successively, chemical polishing, Ultrasonic Cleaning process, then the Ti substrate material after processing is as anode, graphite or Pt electrode are as negative electrode, fluorine-containing inorganic aqueous solution or fluorine-containing organic solution are as electrolyte solution, after processing by electrochemistry anodic oxidation, obtain unformed mesoporous TiO
2membrane electrode; After high-temperature calcination in tube type resistance furnace, obtain having the mesoporous TiO of certain crystal formation again
2membrane electrode, standby;
(2) form visible ray photoelectricity-Fenton system: the mesoporous TiO that step (1) is obtained
2membrane electrode is as anode, and carbonaceous material, as negative electrode, carries out aeration by the aerator target, applies DC voltage-stabilizing and visible ray irradiation simultaneously, forms visible ray photoelectricity-Fenton system;
(3) organic matter is degraded: the organic matter of difficult degradation is placed in to the visible ray photoelectricity that step (2) obtains-Fenton system and is degraded.
2. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (1), the abrasive paper for metallograph that the sand paper that described polishing adopts is 500#, 1000#, 1500#, polishing successively.
3. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (1), the polishing fluid that described chemical polishing adopts is HF: HNO by following raw material and volume ratio
3: H
2o=1: form at 4: 5.
4. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (1), described fluorine-containing inorganic aqueous solution is HF solution, and the mass concentration of HF is 0.2 ~ 0.5 wt%; Described fluorine-containing organic solution is NH
4the mixed liquor of F and glycerine, in fluorine-containing organic solution, the volume ratio of glycerine and water is 1: 9, contains NH
4the mass concentration of F is 0.2 ~ 0.5 wt%.
5. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (1), controlling voltage in described electrochemistry anodic oxidation is 10 ~ 40V, and the distance between plates of anode and negative electrode is 3 ~ 5cm, and anodizing time is 30 ~ 150min.
6. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (1), it is 20 ℃/min that described tube type resistance furnace is controlled programming rate, and calcining heat is 400 ~ 700 ℃, and calcination time is 60 ~ 180 min.
7. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (2), described carbonaceous material is graphite or NACF.
8. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (2), described anode, the negative electrode distance between plates between them is 3 ~ 7cm, and the control anode voltage is 10 ~ 40V.
9. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (2), described aeration control aeration rate is 0.5 ~ 2 L/min; The pH of described visible ray photoelectricity-Fenton system is 2 ~ 4, and the support electrolyte is Na
2sO
4, dosage is 5 ~ 10 g/L; Fe
2+dosage be 0.1 ~ 1 mM.
10. according to claim 1 by visible ray photoelectricity-organic method of Fenton Synergistic degradation, it is characterized in that: in step (2), described visible ray irradiation is external lighting type, and the employing light source is xenon source.
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