CN103964563A - Visible-light photoelectric-Fenton method for efficiently degrading organic substances - Google Patents
Visible-light photoelectric-Fenton method for efficiently degrading organic substances Download PDFInfo
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- CN103964563A CN103964563A CN201410221582.6A CN201410221582A CN103964563A CN 103964563 A CN103964563 A CN 103964563A CN 201410221582 A CN201410221582 A CN 201410221582A CN 103964563 A CN103964563 A CN 103964563A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 title claims abstract description 14
- 230000000593 degrading effect Effects 0.000 title abstract 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 55
- 239000010439 graphite Substances 0.000 claims abstract description 55
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 99
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 238000005273 aeration Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 239000002957 persistent organic pollutant Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 239000002071 nanotube Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000007743 anodising Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000003637 basic solution Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 3
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 43
- 238000005516 engineering process Methods 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000001276 controlling effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000002048 anodisation reaction Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 238000003837 high-temperature calcination Methods 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a visible-light photoelectric-Fenton method for efficiently degrading organic substances. Visible light, TiO2 photocatalysis and electric-Fenton are integrated to constitute a visible-light photoelectric-Fenton system for degrading the organic substances. The method comprises the following steps: preparing a TNTs electrode and a Fe2O3/TNTs electrode; and constituting the visible-light photoelectric-Fenton system by using the TNTs electrode or Fe2O3/TNTs electrode as the anode and graphite or activated carbon fibers as the cathode, and degrading the organic substances. By combining the TiO2 photocatalysis, electrochemical oxidization and Fenton oxidization techniques and introducing visible light to constitute the visible-light photoelectric-Fenton system, the self-made TNTs electrode and Fe2O3/TNTs electrode are used in the visible-light photoelectric-Fenton system, thereby implementing efficient degradation of organic substances under visible light.
Description
Technical field
The invention belongs to environment protection and improvement field, be specifically related to the organic visible ray photoelectricity-Fenton of a kind of efficient degradation method.
Background technology
Photocatalysis technology is a kind of effective way of degraded environmental pollutant, has been widely used in organic degraded in environment.In photocatalysis technology, TiO
2photochemical catalysis relies on its good stability, the advantage such as pollution-free, nontoxic had deep love for by scholar.Yet traditional powder TiO
2that photocatalysis technology still faces is difficult separated without response, catalyzer to visible ray, the easy problem such as compound in electron hole, has limited its further application aspect environmental purification.The proposition of photoelectric technology has well solved that catalyzer is fixed, the separated problem of electron hole, is subject to numerous investigators' favor.Especially based on TiO
2the photoelectrocatalysis technology of nanotube electrode, has been proved to be and has had certain visible light catalytic performance.
Although TiO
2nanotube electrode photoelectrocatalysis technology has made up the deficiency of traditional photocatalysis technology, but the low problem of photocatalysis efficiency still effectively do not solved, and limits it and further applies.For solving TiO
2the problem that nanotube electrode photocatalysis efficiency is low, the combination technology of photocatalysis technology and high-level oxidation technology arises at the historic moment.Electricity-Fenton technology is a kind of efficient treatment process in high-level oxidation technology, by Fenton, is reacted and can be produced the extremely strong OH of oxidisability, and OH contacts with pollutent, is directly oxidized to H
2o, CO
2and small organic molecule, higher to the removal efficiency of pollutent.But the consumption to electric energy is larger, limited to a certain extent its application.Khataee A.R. etc. points out: if by TiO
2nanotube electrode photocatalysis technology is combined with electricity-Fenton technology, not only can solve the problem that photocatalysis efficiency is low, has also solved to a certain extent the large problem of electricity-Fenton process energy consumption.To TiO
2nanotube electrode photocatalysis technology focuses mostly in UV-light with the research that electricity-Fenton technology is combined, UV-light only accounts for a seldom part in sunlight, if visible light application can be had to certain effect in photoelectricity-Fenton reaction system and to the removal of pollutent, will produce inspiration to utilizing sun power to process waste water.
Therefore, prepare the high TiO of photoelectrocatalysis efficiency under visible ray
2nanotube electrode, and it is carried out to visible ray modification, further to improve its response under visible ray, improve the degradation capability of visible ray photoelectricity-Fenton system to pollutent, there is positive meaning.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of organic visible ray photoelectricity-Fenton of the efficient degradation method of processing cost that can improve photocatalysis efficiency, reduce electricity-Fenton, raising visible ray utilization ratio is provided.
The present invention is achieved by the following technical solutions:
The organic visible ray photoelectricity-Fenton of an efficient degradation method, collection visible ray, TiO
2photochemical catalysis and electricity-Fenton, in one, form visible ray photoelectricity-Fenton system, and organism is carried out to efficient degradation, and its concrete operation step is as follows:
(1) anonizing is prepared TiO
2nanotube electrode, i.e. TNTs electrode:
By Ti substrate material polish successively, chemical rightenning, ultrasonic cleaning process, then the Ti substrate material after processing is as anode, Graphite Electrodes is as negative electrode, with containing NH
4f be the glycerol mixing solutions of 0.1～0.5wt% concentration as electrolytic solution, the volume ratio of glycerol and water is 4:1～9:1, adopts the direct current of 10～30V to carry out electrochemical anodic oxidation processing, obtains unformed TNTs electrode after 30～90min; 500～600 ℃ of calcining at constant temperature 60～150min in tube type resistance furnace again, obtain having the TNTs electrode of crystal formation, standby;
(2) cathode electrodeposition is prepared Fe
2o
3modification TiO
2nanotube electrode, i.e. Fe
2o
3/ TNTs electrode:
The TNTs electrode with crystal formation prepared by step (1) is immersed in the ferric salt solution that concentration is 0.025～0.25mmol/L ultrasonic, then transfer in the sulfate liquor that concentration is 0.05～0.2mmol/L, take graphite as anode, TNTs electrode is negative electrode, keep constant voltage 5～15V, carry out galvanic deposit, make Fe
3+uniform deposition, in the pore of TNTs electrode, obtains Fe/TNTs electrode.Using Fe/TNTs electrode as anode again, and noble electrode is negative electrode, and in the alkaline electrolyte that is 0.5～2mol/L in concentration, constant voltage carries out anodic oxidation, makes Fe/TNTs electrode be transformed into corresponding Fe
2o
3/ TNTs electrode;
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The Fe that the TNTs electrode that step (1) is obtained or step (2) obtain
2o
3/ TNTs electrode is as anode, and carbonaceous material, as negative electrode, carries out aeration by aerating apparatus anticathode, applies DC voltage-stabilizing and 150W xenon lamp visible ray irradiation simultaneously, forms visible ray photoelectricity-Fenton system; Utilize visible ray photoelectricity-Fenton system to degrade to organic pollutant.
In described step (1), the crystal formation of TNTs electrode is the mixing crystal formation of anatase octahedrite and rutile.
In described step (2), trivalent iron salt is Fe (NO
3)
39H
2o, Fe
2(SO
4)
39H
2o, FeCl
36H
2a kind of in O; Vitriol is Na
2sO
4or K
2sO
4.
In described step (2), ultrasonic time is 5～20min, electrodeposition time 10～30min.
In described step (2), noble electrode is Pt electrode or Graphite Electrodes, and basic solution is KOH or NaOH, anodizing time 1～5min.
In described step (3), carbonaceous material is graphite or activated carbon fiber, and the distance between plates 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, and the pH of visible ray photoelectricity-Fenton system is 2～5, and support ionogen is NaNO
3or Na
2sO
4, concentration is 1～10g/L, Fe
2+dosage be 0.1～1.5mmol/L.
The present invention is as follows with respect to advantage and the positively effect of prior art:
1, the present invention adopts anonizing on Ti substrate material, to prepare TNTs electrode, can prepare that pattern is regular, the TNTs of size homogeneous, and easy and simple to handle, condition is easily controlled; With TNTs, replace traditional powder TiO
2, the vertical stratification of TNTs electrode, for transmission and the diffusion of electronics provides more convenient passage, has reduced the compound of light induced electron-hole, has also solved powder TiO simultaneously
2the catalyzer that exists difficult separated, easily cause secondary pollution problems.
2, the present invention is combined the photochemical catalysis of TNTs electrode with electricity-Fenton technology, and two systems combine, and synergy, has improved the degradation capability to organic pollutant greatly, forms combination technique theoretical, for organic degraded provides new approach.
3, the present invention carries out modification to the TNTs electrode of preparation, preparation Fe
2o
3/ TNTs electrode, increases its response under visible ray, improve its under visible ray to organic degradation capability.
4, the present invention introduces visible ray, the potential safety hazard having existed while having avoided using UV-light, and required cost is corresponding reduction also, and meanwhile, this system, to utilizing sun power to have positive guiding function, has certain industrial promotional value.
Accompanying drawing explanation
Fig. 1 a is the FE-SEM figure of the TNTs electrode that makes under experiment condition in example 2, and Fig. 1 b is the Fe making under experiment condition in example 2
2o
3the FE-SEM figure of/TNTs electrode.
Fig. 2 is the XRD figure making under experiment condition in example 2, and wherein, curve a is the XRD figure of TNTs electrode, and curve b is Fe
2o
3the XRD figure of/TNTs electrode.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
(1) anonizing is prepared TNTs electrode:
The abrasive paper for metallograph of the Ti of purity >99.6% 500#, 1000#, 1500# for substrate material is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2in the polishing fluid of O=1:4:5, carry out chemical rightenning 30s, then adopt successively acetone, ethanol, pure water to be placed in ultrasonic cleaning machine clean.Ti substrate material after processing is as anode, and Graphite Electrodes is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerol mixing solutions are as electrolytic solution, and the volume ratio of glycerol and water is 9:1, contains NH
4the concentration of F is 0.5wt%.With copper wire, make wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.In this reaction, controlling voltage is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Through heat-up rate, be 20 ℃/min again, calcining temperature is in the tube type resistance furnace of 600 ℃ after high-temperature calcination 120min, obtains having the TNTs electrode of certain crystal formation.
(2) form visible ray photoelectricity-Fenton system and organism degraded:
The TNTs electrode respectively step (1) being obtained is as anode, and Graphite Electrodes material is negative electrode, take rectangle PVC groove as electrolytic reaction groove.The distance between plates of anode and negative electrode is 5cm, the anode voltage of controlling is 20V, by aerating apparatus anticathode, carries out aeration, and control aeration rate is 1.5L/min, applying visible ray irradiation is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (TNTs+ graphite+illumination).
Using the RhB of 20mg/L as needs degradable organic pollutant, put in visible ray photoelectricity-Fenton system and carry out DeR, in reaction process, remain at the uniform velocity and stir, in this system, reaction soln pH is 3, support ionogen is Na
2sO
4dosage be 10g/L; Fe
2+dosage be 1mmol/L.Use respectively visible light photocatalysis system (TNTs+ light source), electricity-Fenton system (TNTs+ graphite), visible ray photoelectricity-Fenton system (TNTs+ graphite+light source) is degraded to RhB, in reaction process, remain at the uniform velocity and stir, 60min to the clearance of RhB for being respectively 4.12%, 44.26%, 68.52%, TNTs photochemical catalysis is combined with electricity-Fenton technology, form in visible ray photoelectricity-Fenton system, treatment effect obviously improves, and clearance adds and large 20.14% than independent photochemical catalysis and electricity-Fenton clearance, show that two systems exist synergy.
Embodiment 2:
(1) anonizing is prepared TNTs electrode:
The abrasive paper for metallograph of the Ti of purity >99.6% 500#, 1000#, 1500# for substrate material is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2in the polishing fluid of O=1:4:5, carry out chemical rightenning 30s, then adopt successively acetone, ethanol, pure water to be placed in ultrasonic cleaning machine clean.Ti substrate material after processing is as anode, and Graphite Electrodes is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerol mixing solutions are as electrolytic solution, and the volume ratio of glycerol and water is 9:1, contains NH
4the concentration of F is 0.5wt%.With copper wire, make wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.In this reaction, controlling voltage is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Through heat-up rate, be 20 ℃/min again, calcining temperature is in the tube type resistance furnace of 600 ℃ after high-temperature calcination 120min, obtains having the TNTs electrode of certain crystal formation.
(2) cathode electrodeposition is prepared Fe
2o
3/ TNTs electrode:
TNTs electrode prepared by (1) is immersed in the Fe (NO of 0.05mol/L
3)
39H
2in O solution, carry out supersound process 10min, then transfer to the Na of 0.1mol/L
2sO
4in solution, take graphite as anode, TNTs electrode are negative electrode, keep 8V constant voltage, galvanic deposit 20min, makes Fe
3+uniform deposition, in the pore of TNTs, obtains Fe/TNTs electrode.Using Fe/TNTs electrode as anode again, and Graphite Electrodes is negative electrode, in the KOH of 1mol/L electrolytic solution, adopts the constant voltage of 8V to carry out anodic oxidation 2min, obtains Fe
2o
3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The TNTs electrode or the Fe that respectively step (1), (2) are obtained
2o
3/ TNTs electrode is as anode, and Graphite Electrodes material is negative electrode, take rectangle PVC groove as electrolytic reaction groove.The distance between plates of anode and negative electrode is 5cm, the anode voltage of controlling is 20V, by aerating apparatus anticathode, carries out aeration, and control aeration rate is 1.5L/min, applying visible ray irradiation is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (TNTs+ graphite+light source, Fe
2o
3/ TNTs+ graphite+light source).By this visible ray photoelectricity-Fenton system, organic pollutant is degraded.
Using the RhB of 20mg/L as needs degradable organic pollutant, put in visible ray photoelectricity-Fenton system and carry out DeR, in reaction process, remain at the uniform velocity and stir, in this system, reaction soln pH is 3, support ionogen is Na
2sO
4dosage be 10g/L; Fe
2+dosage be 1mmol/L.Respectively with visible ray light Fenton system (TNTs+ graphite+light source), visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source) RhB is degraded, remain at the uniform velocity and stir in reaction process, 60min for being respectively 69.15%, 77.29%, carries out after modification the Fe making to the clearance of RhB to TNTs electrode
2o
3/ TNTs electrode is in visible ray photoelectricity-Fenton system, and treatment effect has 8.14% raising compared with TNTs.
Embodiment 3:
(1) anonizing is prepared TNTs electrode:
The abrasive paper for metallograph of the Ti of purity >99.6% 500#, 1000#, 1500# for substrate material is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2in the polishing fluid of O=1:4:5, carry out chemical rightenning 30s, then adopt successively acetone, ethanol, pure water to be placed in ultrasonic cleaning machine clean.Ti substrate material after processing is as anode, and Graphite Electrodes is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerol mixing solutions are as electrolytic solution, and the volume ratio of glycerol and water is 9:1, contains NH
4the concentration of F is 0.5wt%.With copper wire, make wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.In this reaction, controlling voltage is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Through heat-up rate, be 20 ℃/min again, calcining temperature is in the tube type resistance furnace of 600 ℃ after high-temperature calcination 120min, obtains having the TNTs electrode of certain crystal formation.
(2) cathode electrodeposition is prepared Fe
2o
3/ TNTs electrode:
TNTs electrode prepared by (1) is immersed in the Fe of 0.025mol/L
2(SO
4)
39H
2in O solution, carry out supersound process 15min, then transfer to the Na of 0.1mol/L
2sO
4in solution, take graphite as anode, TNTs electrode are negative electrode, keep 10V constant voltage, galvanic deposit 15min, makes Fe
3+uniform deposition, in the pore of TNTs, obtains Fe/TNTs electrode.Using Fe/TNTs electrode as anode again, and Graphite Electrodes is negative electrode, in the KOH of 1mol/L electrolytic solution, adopts the constant voltage of 10V to carry out anodic oxidation 3min, obtains Fe
2o
3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The Fe that step (2) is obtained
2o
3/ TNTs electrode is as anode, using graphite or activated carbon fiber (hereinafter to be referred as ACF) electrode as negative electrode, take rectangle PVC groove as electrolytic reaction groove respectively.The distance between plates of anode and negative electrode is 4cm, and the anode voltage of control is 15V, by aerating apparatus anticathode, carries out aeration, and control aeration rate is 1.0L/min, and applying visible ray irradiation is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source, Fe
2o
3/ TNTs+ACF+ light source).By visible ray photoelectricity-Fenton system, organic pollutant is degraded.
Using the RhB of 10mg/L as needs degradable organic pollutant, put in visible ray photoelectricity-Fenton system and carry out DeR, in reaction process, remain at the uniform velocity and stir, in this system, reaction soln pH is 3, support ionogen is Na
2sO
4dosage be 10g/L; Fe
2+dosage be 1mmol/L.Respectively with visible ray light Fenton system (Fe
2o
3/ TNTs+ graphite+light source), visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ACF+ light source) RhB is degraded, in reaction process, remains at the uniform velocity and to stir, 60min to the clearance of RhB for being respectively 74.15%, 81.33%, with the Fe preparing
2o
3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material becomes ACF from graphite, and treatment effect has 7.18% raising.
Embodiment 4:
(1) anonizing is prepared TNTs electrode:
The abrasive paper for metallograph of the Ti of purity >99.6% 500#, 1000#, 1500# for substrate material is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2in the polishing fluid of O=1:4:5, carry out chemical rightenning 30s, then adopt successively acetone, ethanol, pure water to be placed in ultrasonic cleaning machine clean.Ti substrate material after processing is as anode, and Graphite Electrodes is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerol mixing solutions are as electrolytic solution, and the volume ratio of glycerol and water is 9:1, contains NH
4the concentration of F is 0.5wt%.With copper wire, make wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.In this reaction, controlling voltage is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Through heat-up rate, be 20 ℃/min again, calcining temperature is in the tube type resistance furnace of 600 ℃ after high-temperature calcination 120min, obtains having the TNTs electrode of certain crystal formation.
(2) cathode electrodeposition is prepared Fe
2o
3/ TNTs electrode:
TNTs electrode prepared by (1) is immersed in the FeCl of 0.05mol/L
36H
2in O solution, carry out supersound process 10min, then transfer to the K of 0.1mol/L
2sO
4in solution, take graphite as anode, TNTs electrode are negative electrode, keep 5V constant voltage, galvanic deposit 30min, makes Fe
3+uniform deposition, in the pore of TNTs, obtains Fe/TNTs electrode.Using Fe/TNTs electrode as anode again, and Graphite Electrodes is negative electrode, in the NaOH of 1mol/L electrolytic solution, adopts the constant voltage of 5V to carry out anodic oxidation 5min, obtains Fe
2o
3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The TNTs electrode or the Fe that respectively step (1), (2) are obtained
2o
3/ TNTs electrode is as anode, and Graphite Electrodes material is negative electrode, take rectangle PVC groove as electrolytic reaction groove.The distance between plates of anode and negative electrode is 6cm, the anode voltage of controlling is 30V, by aerating apparatus anticathode, carries out aeration, and control aeration rate is 1.5L/min, applying visible ray irradiation is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (TNTs+ graphite+light source, Fe
2o
3/ TNTs+ graphite+light source).By visible ray photoelectricity-Fenton system, organic pollutant is degraded.
Using the RhB of 30mg/L as needs degradable organic pollutant, put in visible ray photoelectricity-Fenton system and carry out DeR, in reaction process, remain at the uniform velocity and stir, in this system, reaction soln pH is 3, support ionogen is Na
2sO
4dosage be 5g/L; Fe
2+dosage be 1mmol/L.Respectively with visible ray light Fenton system (TNTs+ graphite+light source), visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source) RhB is degraded, remain at the uniform velocity and stir in reaction process, 60min for being respectively 61.68%, 67.69%, carries out after modification the Fe making to the clearance of RhB to TNTs electrode
2o
3/ TNTs electrode is in visible ray photoelectricity-Fenton system, and treatment effect has 6.01% raising compared with TNTs.
Embodiment 5:
(1) anonizing is prepared TNTs electrode:
The abrasive paper for metallograph of the Ti of purity >99.6% 500#, 1000#, 1500# for substrate material is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2in the polishing fluid of O=1:4:5, carry out chemical rightenning 30s, then adopt successively acetone, ethanol, pure water to be placed in ultrasonic cleaning machine clean.Ti substrate material after processing is as anode, and Graphite Electrodes is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerol mixing solutions are as electrolytic solution, and the volume ratio of glycerol and water is 9:1, contains NH
4the concentration of F is 0.5wt%.With copper wire, make wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.In this reaction, controlling voltage is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Through heat-up rate, be 20 ℃/min again, calcining temperature is in the tube type resistance furnace of 600 ℃ after high-temperature calcination 120min, obtains having the TNTs electrode of certain crystal formation.
(2) cathode electrodeposition is prepared Fe
2o
3/ TNTs electrode:
TNTs electrode prepared by (1) is immersed in the Fe of 0.025mol/L
2(SO
4)
39H
2in O solution, carry out supersound process 10min, then transfer to the Na of 0.2mol/L
2sO
4in solution, take graphite as anode, TNTs electrode are negative electrode, keep 5V constant voltage, galvanic deposit 15min, makes Fe
3+uniform deposition, in the pore of TNTs, obtains Fe/TNTs electrode.Using Fe/TNTs electrode as anode again, and Graphite Electrodes is negative electrode, in the KOH of 1mol/L electrolytic solution, adopts the constant voltage of 5V to carry out anodic oxidation 5min, obtains Fe
2o
3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The Fe respectively step (2) being obtained
2o
3/ TNTs electrode is as anode, and graphite or activated carbon fiber (ACF) electrode is negative electrode, take rectangle PVC groove as electrolytic reaction groove.The distance between plates of anode and negative electrode is 4cm, and the anode voltage of control is 30V, by aerating apparatus anticathode, carries out aeration, and control aeration rate is 1.5L/min, and applying visible ray irradiation is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source, Fe
2o
3/ TNTs+ACF+ light source).By visible ray photoelectricity-Fenton system, organic pollutant is degraded.
Using the RhB of 40mg/L as needs degradable organic pollutant, put in visible ray photoelectricity-Fenton system and carry out DeR, in reaction process, remain at the uniform velocity and stir, in this system, reaction soln pH is 3, support ionogen is Na
2sO
4dosage be 5g/L; Fe
2+dosage be 1.5mmol/L.Use respectively visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source), visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ACF+ light source) RhB is degraded, in reaction process, remains at the uniform velocity and to stir, 60min to the clearance of RhB for being respectively 65.58%, 71.18%, with the Fe preparing
2o
3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material becomes ACF from graphite, and treatment effect has 5.60% raising.
Embodiment 6:
(1) anonizing is prepared TNTs electrode:
The abrasive paper for metallograph of the Ti of purity >99.6% 500#, 1000#, 1500# for substrate material is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2in the polishing fluid of O=1:4:5, carry out chemical rightenning 30s, then adopt successively acetone, ethanol, pure water to be placed in ultrasonic cleaning machine clean.Ti substrate material after processing is as anode, and Graphite Electrodes is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerol mixing solutions are as electrolytic solution, and the volume ratio of glycerol and water is 9:1, contains NH
4the concentration of F is 0.5wt%.With copper wire, make wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.In this reaction, controlling voltage is 20V, and anodizing time is 90min, obtains unformed TNTs electrode; Through heat-up rate, be 20 ℃/min again, calcining temperature is in the tube type resistance furnace of 500 ℃ after high-temperature calcination 150min, obtains having the TNTs electrode of certain crystal formation.
(2) cathode electrodeposition is prepared Fe
2o
3/ TNTs electrode:
TNTs electrode prepared by (1) is immersed in the Fe of 0.25mol/L
2(SO
4)
39H
2in O solution, carry out supersound process 5min, then transfer to the Na of 0.05mol/L
2sO
4in solution, take Pt as anode, TNTs electrode are negative electrode, keep 15V constant voltage, galvanic deposit 10min, makes Fe
3+uniform deposition, in the pore of TNTs, obtains Fe/TNTs electrode.Using Fe/TNTs electrode as anode again, and Graphite Electrodes is negative electrode, in the KOH of 0.5mol/L electrolytic solution, adopts the constant voltage of 15V to carry out anodic oxidation 1min, obtains Fe
2o
3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The Fe respectively step (2) being obtained
2o
3/ TNTs electrode is as anode, and graphite and activated carbon fiber (ACF) electrode is negative electrode, take rectangle PVC groove as electrolytic reaction groove.The distance between plates of anode and negative electrode is 2cm, and the anode voltage of control is 5V, by aerating apparatus anticathode, carries out aeration, and control aeration rate is 0.5L/min, and applying visible ray irradiation is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source, Fe
2o
3/ TNTs+ACF+ light source).By visible ray photoelectricity-Fenton system, organic pollutant is degraded.
Using the RhB of 40mg/L as needs degradable organic pollutant, put in visible ray photoelectricity-Fenton system and carry out DeR, in reaction process, remain at the uniform velocity and stir, in this system, reaction soln pH is 3, support ionogen is NaNO
3dosage be 5g/L; Fe
2+dosage be 0.1mmol/L.Use respectively visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source), visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ACF+ light source) RhB is degraded, in reaction process, remains at the uniform velocity and to stir, 60min to the clearance of RhB for being respectively 41.17%, 46.66%, with the Fe preparing
2o
3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material becomes ACF from graphite, and treatment effect has 5.49% raising.
Embodiment 7:
(1) anonizing is prepared TNTs electrode:
The abrasive paper for metallograph of the Ti of purity >99.6% 500#, 1000#, 1500# for substrate material is polished successively, until smooth surface, then to immerse volume ratio be HF:HNO
3: H
2in the polishing fluid of O=1:4:5, carry out chemical rightenning 30s, then adopt successively acetone, ethanol, pure water to be placed in ultrasonic cleaning machine clean.Ti substrate material after processing is as anode, and Graphite Electrodes is as negative electrode, and the distance between plates of anode and negative electrode is 4cm, uses NH
4f and glycerol mixing solutions are as electrolytic solution, and the volume ratio of glycerol and water is 4:1, contains NH
4the concentration of F is 0.1wt%.With copper wire, make wire two-stage is connected on D.C. regulated power supply, carry out electrochemical anodization reaction.In this reaction, controlling voltage is 20V, and anodizing time is 30min, obtains unformed TNTs electrode; Through heat-up rate, be 20 ℃/min again, calcining temperature is in the tube type resistance furnace of 600 ℃ after high-temperature calcination 60min, obtains having the TNTs electrode of certain crystal formation.
(2) cathode electrodeposition is prepared Fe
2o
3/ TNTs electrode:
TNTs electrode prepared by (1) is immersed in the Fe of 0.25mol/L
2(SO
4)
39H
2in O solution, carry out supersound process 20min, then transfer to the Na of 0.15mol/L
2sO
4in solution, take Pt as anode, TNTs electrode are negative electrode, keep 10V constant voltage, galvanic deposit 10min, makes Fe
3+uniform deposition, in the pore of TNTs, obtains Fe/TNTs electrode.Using Fe/TNTs electrode as anode again, and Pt electrode is negative electrode, in the KOH of 2mol/L electrolytic solution, adopts the constant voltage of 10V to carry out anodic oxidation 2min, obtains Fe
2o
3/ TNTs electrode.
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The Fe respectively step (2) being obtained
2o
3/ TNTs electrode is as anode, and graphite and activated carbon fiber (ACF) electrode is negative electrode, take rectangle PVC groove as electrolytic reaction groove.The distance between plates of anode and negative electrode is 6cm, and the anode voltage of control is 10V, by aerating apparatus anticathode, carries out aeration, and control aeration rate is 2.5L/min, and applying visible ray irradiation is 150W xenon lamp, forms visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ graphite+light source, Fe
2o
3/ TNTs+ACF+ light source).By visible ray photoelectricity-Fenton system, organic pollutant is degraded.
Using the RhB of 40mg/L as needs degradable organic pollutant, put in visible ray photoelectricity-Fenton system and carry out DeR, in reaction process, remain at the uniform velocity and stir, in this system, reaction soln pH is 5, support ionogen is NaNO
3dosage be 5g/L; Fe
2+dosage be 1.5mmol/L.Respectively with visible ray light Fenton system (Fe
2o
3/ TNTs+ graphite+light source), visible ray photoelectricity-Fenton system (Fe
2o
3/ TNTs+ACF+ light source) RhB is degraded, in reaction process, remains at the uniform velocity and to stir, 60min to the clearance of RhB for being respectively 42.22%, 48.66%, with the Fe preparing
2o
3/ TNTs electrode is the anode of visible ray photoelectricity-Fenton system, and cathode material becomes ACF from graphite, and treatment effect has 6.44% raising.
Claims (7)
1. the organic visible ray photoelectricity-Fenton of an efficient degradation method, is characterized in that, collection visible ray, TiO
2photochemical catalysis and electricity-Fenton, in one, form visible ray photoelectricity-Fenton system, and organism is carried out to efficient degradation, and its concrete operation step is as follows:
(1) anonizing is prepared TiO
2nanotube electrode, i.e. TNTs electrode:
By Ti substrate material polish successively, chemical rightenning, ultrasonic cleaning process, then the Ti substrate material after processing is as anode, Graphite Electrodes is as negative electrode, with containing NH
4f be the glycerol mixing solutions of 0.1～0.5wt% concentration as electrolytic solution, the volume ratio of glycerol and water is 4:1～9:1, adopts the direct current of 10～30V to carry out electrochemical anodic oxidation processing, obtains unformed TNTs electrode after 30～90min; 500～600 ℃ of calcining at constant temperature 60～150min in tube type resistance furnace again, obtain having the TNTs electrode of crystal formation, standby;
(2) cathode electrodeposition is prepared Fe
2o
3modification TiO
2nanotube electrode, i.e. Fe
2o
3/ TNTs electrode:
The TNTs electrode with crystal formation prepared by step (1) is immersed in the ferric salt solution that concentration is 0.025～0.25mmol/L ultrasonic, then transfer in the sulfate liquor that concentration is 0.05～0.2mmol/L, take graphite as anode, TNTs electrode is negative electrode, keep constant voltage 5～15V, carry out galvanic deposit, make Fe
3+uniform deposition, in the pore of TNTs electrode, obtains Fe/TNTs electrode; Using Fe/TNTs electrode as anode again, and noble electrode is negative electrode, and in the alkaline electrolyte that is 0.5～2mol/L in concentration, constant voltage carries out anodic oxidation, makes Fe/TNTs electrode be transformed into corresponding Fe
2o
3/ TNTs electrode;
(3) form visible ray photoelectricity-Fenton system and organism degraded:
The Fe that the TNTs electrode that step (1) is obtained or step (2) obtain
2o
3/ TNTs electrode is as anode, and carbonaceous material, as negative electrode, carries out aeration by aerating apparatus anticathode, applies DC voltage-stabilizing and 150W xenon lamp visible ray irradiation simultaneously, forms visible ray photoelectricity-Fenton system; Utilize visible ray photoelectricity-Fenton system to degrade to organic pollutant.
2. the organic visible ray photoelectricity-Fenton of efficient degradation according to claim 1 method, is characterized in that, in described step (1), the crystal formation of TNTs electrode is the mixing crystal formation of anatase octahedrite and rutile.
3. the organic visible ray photoelectricity-Fenton of efficient degradation according to claim 1 method, is characterized in that, in described step (2), trivalent iron salt is Fe (NO
3)
39H
2o, Fe
2(SO
4)
39H
2o or FeCl
36H
2a kind of in O; Vitriol is Na
2sO
4or K
2sO
4.
4. the organic visible ray photoelectricity-Fenton of efficient degradation according to claim 1 method, is characterized in that, in described step (2), ultrasonic time is 5～20min, electrodeposition time 10～30min.
5. the organic visible ray photoelectricity-Fenton of efficient degradation according to claim 1 method, is characterized in that, in described step (2), noble electrode is Pt electrode or Graphite Electrodes, and basic solution is KOH or NaOH, anodizing time 1～5min.
6. the organic visible ray photoelectricity-Fenton of efficient degradation according to claim 1 method, it is characterized in that, in described step (3), carbonaceous material is graphite or activated carbon fiber, distance between plates between anode and negative electrode is 2～6cm, and control anode voltage is 5～30V.
7. the organic visible ray photoelectricity-Fenton of efficient degradation according to claim 1 method, it is characterized in that, in described step (3), aeration control aeration rate is 0.5～2.5L/min, the pH of visible ray photoelectricity-Fenton system is 2～5, and support ionogen is NaNO
3or Na
2sO
4, concentration is 1～10g/L, Fe
2+dosage be 0.1～1.5mmol/L.
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| CN101429673A (en) * | 2008-11-26 | 2009-05-13 | 天津大学 | Method for producing titanium dioxide nano pipe array by anodization method with aseptic |
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| CN101429673A (en) * | 2008-11-26 | 2009-05-13 | 天津大学 | Method for producing titanium dioxide nano pipe array by anodization method with aseptic |
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