CN107200383A - A kind of method that selective light electrocatalytic oxidation removes Atrazine - Google Patents
A kind of method that selective light electrocatalytic oxidation removes Atrazine Download PDFInfo
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- CN107200383A CN107200383A CN201710516704.8A CN201710516704A CN107200383A CN 107200383 A CN107200383 A CN 107200383A CN 201710516704 A CN201710516704 A CN 201710516704A CN 107200383 A CN107200383 A CN 107200383A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of method that selective light electrocatalytic oxidation removes Atrazine, the molecular engram meso-porous titanium dioxide Ti electrode prepared in the method for evaporation induced self-assembly and binding molecule trace is working electrode, using platinum plate electrode as to electrode, saturated calomel electrode (SCE) is reference electrode, high pressure xenon lamp is excitation source, it is 1cm with the spacing to electrode to keep working electrode, under conditions of being biased, photoelectrocatalysioxidization oxidization removal is carried out to the Atrazine in the aqueous solution containing supporting electrolyte in electrolytic cell.Compared with prior art, the clearance 93.9% of working electrode surface Atrazine of the present invention, apparent reaction rate constant is 0.28h‑1.In actual environment waste water, MI meso TiO2The removal efficiency of electrode surface Atrazine is 92%, and apparent reaction rate constant is 0.25h‑1；Apparently higher than meso TiO2Effect (clearance is 57%；Apparent reaction rate constant is 0.09h‑1)。
Description
Technical field
The present invention relates to photo-electrocatalytic technology field, more particularly, to point with high selectivity photoelectrocatalysioxidization oxidization performance
Sub- trace type meso-porous titanium dioxide Ti electrode MI-meso-TiO2Preparation method and its high selectivity depth in environmental contaminants
The application in removal field.
Background technology
Photocatalysis technology is gentle because of reaction condition, and oxidability has been widely used for by force the processing of environmental wastewater, but light
Semiconductor photoproduction electron hole pair is easily combined again in catalytic process, and this problem reduces photocatalytic oxidation efficiency, therefore must
The capture of photo-generate electron-hole must be increased or surface charge migration rate is improved, suppress the compound of electron-hole, make photoproduction electricity
Son and hole are utilized effectively, and improve catalytic efficiency.
Photo-electrocatalytic technology, using the material with excellent photocatalysis performance as optoelectronic pole, and is biased promotion photoelectricity
Electronics and the separation in hole, so as to greatly improve the catalytic efficiency of photocatalysis technology, are highly suitable for the oxygen of pollutant in water body
Change and remove, the depth for being particularly suitable for low concentration pollutant in water body is removed.
But application of the photo-electrocatalytic technology in actual water body is restricted, reason is that the technology does not have to substrate in itself
Selectivity, almost can oxidative degradation absorption catalyst surface any organic pollution.In actual water body, the species of pollutant
Numerous and diverse, toxicity is different, and concentration is different, and the concentration of general low toxicity or nontoxic pollutant in water body is compared to high toxicity pollutant
Will height.Therefore, because the difference of concentration, these pollutants can produce competitive reaction in catalyst surface.It is obvious that high concentration
Pollutant is easier absorption and preferentially got rid of in catalyst surface, and really needs the highly toxic pollutant removed can not
Degraded in time.Based on this, we must solve the selective problems of photo-electrocatalytic technology.
Chinese patent CN101050000A discloses a kind of method for removing Atrazine in water removal, using dielectric barrier discharge
Method is handled water containing Atrazine, by the Atrazine degradation in water body；The water of processing will be needed to be put into high-field electrode
Between grounding electrode, separately there is medium between the water surface and high-field electrode, the electric current exported by high frequency electric source is passed through high-tension electricity
Pole, carries out dielectric barrier discharge, water is handled；The electric current wherein discharged is produced by high frequency electric source, and discharge voltage peak value is
8000~12000V, maximum discharge current is 20~50MA, and the power frequency of generation is 2.5KHZ~30KHZ；Dielectric impedance is put
The medium of electricity and the distance of the water surface are no more than 20MM.The patent uses dielectric barrier discharge method to realize Atrazine in water body
Removal, the voltage and power for inputting high frequency electric source are adjusted by adjuster, power and voltage is higher, the degraded effect of Atrazine
Fruit is better.Comparatively speaking, if wanting to obtain preferable removal effect, this method power consumption is obvious.In addition, the activity that this method is produced
Reacted with the pollutant in water body to material non-selectivity, it is impossible to realize selective removal Atrazine, limit its
Application in complicated actual water body in specific pollutants removal field.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of fusion molecule trace
The method that a kind of selective light electrocatalytic oxidation of technology and photoelectro-catalytic oxidation technology removes Atrazine.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method that selective light electrocatalytic oxidation removes Atrazine, with evaporation induced self-assembly and combination point
The molecular engram meso-porous titanium dioxide Ti electrode that the method for sub- trace is prepared is working electrode, using platinum plate electrode as to electrode,
Saturated calomel electrode (SCE) is reference electrode, and high pressure xenon lamp is excitation source, and it is 1- with the spacing to electrode to keep working electrode
3cm, under conditions of (0.6-1.4V) is biased, to the Atrazine in the aqueous solution containing supporting electrolyte in electrolytic cell
Carry out photoelectrocatalysioxidization oxidization removal.Described electrolytic cell makes temperature of reaction system be maintained at 25-30 DEG C using constant temperature water bath apparatus,
Optical intensity density 130-170mW/cm2。
Described molecular engram meso-porous titanium dioxide Ti electrode is prepared using following methods：
(1) titanium plate of well cutting is successively used 180#、320#、600#, abrasive paper for metallograph polishing, until surface is smooth, without drawing
Trace, is cleaned the titanium plate polished with distilled water, is cleaned by ultrasonic successively with distilled water, ethanol, acetone afterwards to surface cleaning, most
Clean titanium plate is put into 100 DEG C of 10wt% oxalic acid solutions afterwards, 20~30min is kept, taken out and clean with distilled water flushing, nitrogen
Air-blowing is done standby；
(2) by P123 and Atrazine dissolving in ethanol, 0.5~1h is stirred at room temperature, it is ensured that P123 and Atrazine fill
It is allocated as using, 37wt% hydrochloric acid and butyl titanate is added dropwise to thereto, 1.5~3h is stirred at room temperature and obtains sol solution；
(3) sol solution prepared is supported on by way of Best-Effort request in the titanium plate handled well, then will system
The electrode got ready places 12~24h at ambient temperature；
(4) photoelectrocatalysielectrode electrode prepared is heat-treated by the way of temperature programming in tube furnace, obtained
Molecular engram meso-porous titanium dioxide Ti electrode.
The mol ratio of P123 and Atrazine is 1 in step (2)：1.4~1：1.6, mole of hydrochloric acid and butyl titanate
Than for 1：1.7~1：2.
Controlled in step (3) during Best-Effort request the rate of climb be 2000-3000 μm/s, decrease speed be 2000-3000 μm/
S, the residence time of electrode in the solution is 5~10min.
Heat treatment rises to 450~550 DEG C of 1~3h of heat treatment by 0.5~3 DEG C/min heating rate in step (4).
The described aqueous solution is that concentration is 10mg L-1Atrazine solution, supporting electrolyte be 0.1mol L-1Na2SO4
Solution.
The described aqueous solution is Atrazine and chaff interference 2, and 4-D concentration is 10mg L-1Solution, supporting electrolyte
For 0.1mol L-1Na2SO4Solution.
The described aqueous solution is actual waste water, and COD is 30~40ppm, target stains 2~3ppm of Atrazine, supports electricity
Solution matter is 0.1mol L-1Na2SO4Solution.
Compared with prior art, the present invention combines photo-electrocatalytic technology and molecular imprinting technology, realizes photoelectrocatalysis
Selectivity.The method that we utilize simple evaporation-induced self-assembly, mesh is carried out while meso-porous titanium dioxide Ti electrode is prepared
Mark the design of thing molecular engram structure and construct, keep original meso-TiO2Pole while electrode efficient photoelectricity treater catalytic activity
The earth improves the selective catalytic oxidation ability of electrode, toxicity different the characteristics of system numerous and diverse for pollutant kind in environment
For a kind of novel electrode with excellent photoelectrocatalysis selection performance is gone out, with advantages below：
(1) fusion molecule engram technology and photoelectro-catalytic oxidation technology of the present invention, the MI-meso-TiO prepared2Electricity
Pole can the corresponding target substance of specific adsorption, solve photoelectrocatalysis react non-selectivity problem, realize selectivity
Photoelectrocatalysioxidization oxidization Atrazine.Solve the drop that traditional method for treating water is unable to low concentration pollutant in selective removal water body
Solution problem.
(2) meso-TiO with unmodified Atrazine molecular engram site is passed through2Electrode pair ratio, MI-meso-TiO2Go
It is meso-TiO except rate (93.9%)21.35 times；Speed constant (0.28h-1) it is meso-TiO22.3 times.
(3) MI-meso-TiO in the system that target contaminant Atrazine and chaff interference 2,4-D coexist with concentration2Electricity
Extremely there is good selectivity to Atrazine.Coexist in system, MI-meso-TiO2Electrode surface Atrazine clearance is
90.8%, speed constant is 0.23h-1, chaff interference 2,4-D presence on the degradation effect influence of electrode surface Atrazine very
It is small.
(4) present invention can be imprinted templates by introducing other specific pollutants molecules in electrode production process,
The electrode to the molecule with specific recognition capability is obtained, the selective light electrocatalytic oxidation of corresponding target contaminant is realized
Change, method has universality.
Brief description of the drawings
Fig. 1 is the MI-meso-TiO prepared2The scanning electron microscope (SEM) photograph of electrode；
Fig. 2 is the MI-meso-TiO prepared2And meso-TiO2The removal effect of Atrazine in electrode surface actual waste water
Really.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.Following examples will be helpful to this area
Technical staff further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the general of this area
For logical technical staff, without departing from the inventive concept of the premise, various modifications and improvements can be made.These are belonged to
Protection scope of the present invention.
Embodiment 1
The Ti bases of well cutting are successively used 180#、320#、600#, abrasive paper for metallograph polishing, until surface is smooth, no marking.
The titanium plate polished is cleaned with distilled water first, then cleaned successively with acetone, ethanol, distilled water, it is each to be cleaned by ultrasonic
15min, to surface cleaning.Finally, clean titanium plate is put into 100 DEG C of 10% oxalic acid solution, 20~30min is kept, taken out
And it is clean with distilled water flushing, nitrogen drying is standby.0.2mmol P123 and 0.287mmol Atrazines are weighed to be dissolved in
In 0.26mol ethanol, 0.5h is stirred at room temperature；Into the above-mentioned solution being stirred add 25.6mmol hydrochloric acid (37%) and
14.12mmol butyl titanates, are stirred at room temperature 1.5h and obtain sol solution.Afterwards, the sol solution prepared is passed through into dipping
The mode of lifting is supported in the titanium plate handled well, the rate of climb be 2000-3000 μm/s, decrease speed be 2000-3000 μm/
S, the residence time of electrode in the solution is 5~10min；12h is placed under room temperature condition.By the catalyst prepared in tube furnace
It is middle to be heat-treated by the way of temperature programming, i.e., rise to 450 DEG C of heat treatment 0.5h by 0.7 DEG C/min heating rate；Obtain
There must be the meso-porous titanium dioxide Ti electrode in molecular engram site.The MI-meso-TiO of preparation2The scanning electron microscope (SEM) photograph (SEM) of electrode
As shown in Figure 1.
Embodiment 2
The experiment of photoelectrocatalysioxidization oxidization Atrazine is carried out in the mono- pond circular quartz electrolytic cells of 100mL, and additional carry is followed
The a set of cups of ring water system, makes temperature of reaction system be maintained at 25 DEG C.With MI-meso-TiO2For working electrode, platinum plate electrode for pair
Electrode, saturated calomel electrode (SCE) is reference electrode.Working electrode (puts and is placed in after quartz ampoule in solution) distance with light source
6.0cm, geometric area is 15cm2, keep working electrode and be 1cm to spacing between electrode, the bias of application is+0.6V, real
It is high pressure xenon lamp to test the middle light source used.Target stains atrazine concentration is 10mg L-1, supporting electrolyte is 0.1mol L- 1Na2SO4Solution, processing volume is 90mL.Electrode is immersed in 30min in solution before reaction, it is ensured that electrode surface absorption reaches
To balance.The equilibrium concentration of solution now is taken as initial concentration, sampling analysis at the time of oxidation reaction proceeds to different.With
The concentration that HPLC determines two electrode surface Atrazines in oxidizing process changes with time trend (acetonitrile and water volume ratio 60：
40, flow velocity 1mL min-1, sample size 20 μ L, Detection wavelength 220nm).As a result show, in photoelectrocatalysioxidization oxidization Atrazine
After 600min, MI-meso-TiO2The degradation efficiency of electrode surface Atrazine is 93.9%, and reaction rate constant is 0.28h-1。
Embodiment 3
Photoelectrocatalysioxidization oxidization experiment is carried out in the mono- pond circular quartz electrolytic cells of 100mL, additional to carry circulation
A set of cups, makes temperature of reaction system be maintained at 25 DEG C.MI-meso-TiO2For working electrode, platinum plate electrode is that saturation is sweet to electrode
Mercury electrode (SCE) is reference electrode.Working electrode is with light source (put and be placed in after quartz ampoule in solution) apart from 6.0cm, geometric surface
Product is 15cm2, keep working electrode and be 1cm to spacing between electrode, the bias of application is+0.6V, the light used in experiment
Source is high pressure xenon lamp.Target substance Atrazine and chaff interference 2 in oxidation reaction system, 4-D coexists, and concentration is 10mg L-1,
Supporting electrolyte is 0.1mol L-1Na2SO4Solution, processing volume is 90mL.Electrode is immersed in solution before reaction
30min, it is ensured that electrode surface absorption reaches balance.The equilibrium concentration of solution now is taken as initial concentration, is carried out in oxidation reaction
To it is different at the time of sampling analysis.Changed with time with the HPLC concentration for determining two electrode surface Atrazines in oxidizing process
Trend (acetonitrile and water volume ratio 60：40, flow velocity 1mL min-1, sample size 20 μ L, Detection wavelength 220nm).As a result show, in light
After electrocatalytic oxidation Atrazine 600min, MI-meso-TiO2Its degradation efficiency of electrode pair is 90.8%.
Embodiment 4
The water sample that we use is taken from Quyang sewage treatment plant, and COD is 30ppm.And 2ppm Aunar is added wherein
Tianjin is drawn to be used as goal in research, 0.1mol L-1Na2SO4For supporting electrolyte.Photoelectrocatalysioxidization oxidization experiment is circular in the mono- ponds of 100mL
Carried out in quartzy electrolytic cell, the additional a set of cups with circulation makes temperature of reaction system be maintained at 25 DEG C.MI-meso-
TiO2Electrode is working electrode, and platinum plate electrode is that, to electrode, saturated calomel electrode (SCE) is reference electrode.Working electrode and light
Source (put and be placed in after quartz ampoule in solution) is apart from 6.0cm, and geometric area is 15cm2, keep working electrode and between electrode
Spacing is 1cm, and the bias of application is+0.6V, and the light source used in experiment is high pressure xenon lamp, and processing volume is 90mL.React it
It is preceding that electrode is immersed in 30min in solution, it is ensured that electrode surface absorption reaches balance.The equilibrium concentration of solution now is taken as initially
Concentration, samples at the time of oxidation reaction proceeds to different and is analyzed.Two electrode tables in oxidation reaction process are determined with HPLC
The concentration of face Atrazine changes with time trend (acetonitrile and water volume ratio 60：40, flow velocity 1mL min-1, the μ L of sample size 20,
Detection wavelength 220nm).As a result show, after photoelectrocatalysioxidization oxidization Atrazine 600min, MI-meso-TiO2Electrode surface Ah
Te Lajin clearance is 92%, and dynamics are 0.25h-1, as shown in Fig. 2 figure A is MI-meso-TiO2And meso-TiO2
The clearance of Atrazine in electrode surface actual waste water, figure B is MI-meso-TiO2And meso-TiO2Electrode surface is actual useless
The removal rate constant of Atrazine, wherein meso-TiO in water2Electrode is simple meso-porous titanium dioxide Ti electrode.
Embodiment 5
A kind of method that selective light electrocatalytic oxidation removes Atrazine, with evaporation induced self-assembly and combination point
The molecular engram meso-porous titanium dioxide Ti electrode that the method for sub- trace is prepared is working electrode, using platinum plate electrode as to electrode,
Saturated calomel electrode (SCE) is reference electrode, and high pressure xenon lamp is excitation source, optical intensity density 130mW/cm2.Keep working electrode
It is 1cm with the spacing to electrode, under conditions of 0.6V is biased, in the aqueous solution containing supporting electrolyte in electrolytic cell
Atrazine carry out photoelectrocatalysioxidization oxidization removal, the aqueous solution used is that concentration is 10mg L-1Atrazine solution, support
Electrolyte is 0.1mol L-1Na2SO4Solution.Electrolytic cell makes temperature of reaction system be maintained at 25 DEG C using constant temperature water bath apparatus.
The molecular engram meso-porous titanium dioxide Ti electrode used is prepared using following methods：
(1) titanium plate of well cutting is successively used 180#、320#、600#, abrasive paper for metallograph polishing, until surface is smooth, without drawing
Trace, is cleaned the titanium plate polished with distilled water, is cleaned by ultrasonic successively with distilled water, ethanol, acetone afterwards to surface cleaning, most
Clean titanium plate is put into 100 DEG C of 10wt% oxalic acid solutions afterwards, 20min is kept, taken out and clean with distilled water flushing, nitrogen blows
It is dry standby；
(2) by P123 and Atrazine dissolving in ethanol, the mol ratio of P123 and Atrazine is 1：1.4, room temperature is stirred
Mix 0.5h, it is ensured that P123 and Atrazine are fully acted on, be added dropwise to 37wt% hydrochloric acid and butyl titanate thereto, hydrochloric acid and
The mol ratio of butyl titanate is 1：1.7,1.5h is stirred at room temperature and obtains sol solution；
(3) sol solution prepared is supported on by way of Best-Effort request in the titanium plate handled well, Best-Effort request
When control the rate of climb be 2000 μm/s, decrease speed be 2000 μm/s, the residence time of electrode in the solution be 5min, then
The electrode prepared is placed into 12h at ambient temperature；
(4) photoelectrocatalysielectrode electrode prepared is heat-treated by the way of temperature programming in tube furnace, passed through
0.5 DEG C/min heating rate rises to 450 DEG C of heat treatment 3h, obtains molecular engram meso-porous titanium dioxide Ti electrode.
Embodiment 6
A kind of method that selective light electrocatalytic oxidation removes Atrazine, with evaporation induced self-assembly and combination point
The molecular engram meso-porous titanium dioxide Ti electrode that the method for sub- trace is prepared is working electrode, using platinum plate electrode as to electrode,
Saturated calomel electrode (SCE) is reference electrode, and high pressure xenon lamp is excitation source, optical intensity density 170mW/cm2.Keep working electrode
It is 3cm with the spacing to electrode, under conditions of 1.4V is biased, in the aqueous solution containing supporting electrolyte in electrolytic cell
Atrazine carry out photoelectrocatalysioxidization oxidization removal, the aqueous solution used be actual waste water, COD be 30~40ppm, target stains
2~3ppm of Atrazine, supporting electrolyte is 0.1mol L-1Na2SO4Solution.Electrolytic cell makes reaction using constant temperature water bath apparatus
System temperature is maintained at 30 DEG C.
Molecular engram meso-porous titanium dioxide Ti electrode is prepared using following methods：
(1) titanium plate of well cutting is successively used 180#、320#、600#, abrasive paper for metallograph polishing, until surface is smooth, without drawing
Trace, is cleaned the titanium plate polished with distilled water, is cleaned by ultrasonic successively with distilled water, ethanol, acetone afterwards to surface cleaning, most
Clean titanium plate is put into 100 DEG C of 10wt% oxalic acid solutions afterwards, 30min is kept, taken out and clean with distilled water flushing, nitrogen blows
It is dry standby；
(2) by P123 and Atrazine dissolving in ethanol, the mol ratio of P123 and Atrazine is 1：1.6, room temperature is stirred
Mix 1h, it is ensured that P123 and Atrazine are fully acted on, 37wt% hydrochloric acid and butyl titanate, hydrochloric acid and titanium are added dropwise to thereto
The mol ratio of sour four butyl esters is 1：2,3h is stirred at room temperature and obtains sol solution；
(3) sol solution prepared is supported on by way of Best-Effort request in the titanium plate handled well, Best-Effort request
When control the rate of climb be 3000 μm/s, decrease speed be 3000 μm/s, the residence time of electrode in the solution be 0min then
The electrode prepared is placed into 24h at ambient temperature；
(4) photoelectrocatalysielectrode electrode prepared is heat-treated by the way of temperature programming in tube furnace, at heat
Reason rises to 550 DEG C of heat treatment 3h by 3 DEG C/min heating rate, obtains molecular engram meso-porous titanium dioxide Ti electrode.
The above-mentioned description to example is understood that for ease of those skilled in the art and using the present invention.It is ripe
Know the personnel of art technology obviously can easily make various modifications to these examples, and General Principle described herein
It is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to examples of implementation here, ability
Field technique personnel are according to the announcement of the present invention, and the improvement made for the present invention and modification all should be in protection scope of the present invention
Within.
Claims (10)
1. a kind of method that selective light electrocatalytic oxidation removes Atrazine, it is characterised in that this method is lured with solvent evaporation
It is working electrode to lead the molecular engram meso-porous titanium dioxide Ti electrode that the method for self assembly and binding molecule trace prepares, with platinum
Plate electrode is that to electrode, saturated calomel electrode (SCE) is reference electrode, and high pressure xenon lamp is excitation source, keep working electrode with
Be 1-3cm to the spacing of electrode, under conditions of being biased, in the aqueous solution containing supporting electrolyte in electrolytic cell Ah
Te Lajin carries out photoelectrocatalysioxidization oxidization removal.
2. the method that a kind of selective light electrocatalytic oxidation according to claim 1 removes Atrazine, it is characterised in that
The bias of application is 0.6-1.4V.
3. the method that a kind of selective light electrocatalytic oxidation according to claim 1 removes Atrazine, it is characterised in that
Described electrolytic cell makes temperature of reaction system be maintained at 25-30 DEG C, optical intensity density 130-170mW/ using constant temperature water bath apparatus
cm2。
4. the method that a kind of selective light electrocatalytic oxidation according to claim 1 removes Atrazine, it is characterised in that
Described molecular engram meso-porous titanium dioxide Ti electrode is prepared using following methods：
(1) titanium plate of well cutting is successively used 180#、320#、600#, abrasive paper for metallograph polishing, until surface is smooth, no marking is used
Distilled water cleans the titanium plate polished, and is cleaned by ultrasonic successively with distilled water, ethanol, acetone to surface cleaning afterwards, finally will
Clean titanium plate is put into 100 DEG C of 10wt% oxalic acid solutions, keeps 20~30min, takes out and clean with distilled water flushing, nitrogen blows
It is dry standby；
(2) by P123 and Atrazine dissolving in ethanol, 0.5~1h is stirred at room temperature, it is ensured that P123 and Atrazine are fully made
With being added dropwise to 37wt% hydrochloric acid and butyl titanate thereto, 1.5~3h be stirred at room temperature and obtains sol solution；
(3) sol solution prepared is supported on by way of Best-Effort request in the titanium plate handled well, then will prepared
Electrode place 12~24h at ambient temperature；
(4) photoelectrocatalysielectrode electrode prepared is heat-treated by the way of temperature programming in tube furnace, obtains molecule
Trace meso-porous titanium dioxide Ti electrode.
5. the method that a kind of selective light electrocatalytic oxidation according to claim 4 removes Atrazine, it is characterised in that
The mol ratio of P123 and Atrazine is 1 in step (2)：1.4~1：1.6, the mol ratio of hydrochloric acid and butyl titanate is 1：1.7
~1：2.
6. the method that a kind of selective light electrocatalytic oxidation according to claim 4 removes Atrazine, it is characterised in that
It is 2000-3000 μm/s to control the rate of climb in step (3) during Best-Effort request, and decrease speed is 2000-3000 μm/s, and electrode exists
Residence time in solution is 5~10min.
7. the method that a kind of selective light electrocatalytic oxidation according to claim 4 removes Atrazine, it is characterised in that
Heat treatment rises to 450~550 DEG C of 1~3h of heat treatment by 0.5~3 DEG C/min heating rate in step (4).
8. the method that a kind of selective light electrocatalytic oxidation according to claim 1 removes Atrazine, it is characterised in that
The described aqueous solution is that concentration is 10mg L-1Atrazine solution, supporting electrolyte be 0.1mol L-1Na2SO4Solution.
9. the method that a kind of selective light electrocatalytic oxidation according to claim 1 removes Atrazine, it is characterised in that
The described aqueous solution is Atrazine and chaff interference 2, and 4-D concentration is 10mg L-1Solution, supporting electrolyte is 0.1mol
L-1Na2SO4Solution.
10. the method that a kind of selective light electrocatalytic oxidation according to claim 1 removes Atrazine, its feature exists
It is actual waste water in, the described aqueous solution, COD is 30~40ppm, target stains 2~3ppm of Atrazine, supporting electrolyte is
0.1mol L-1Na2SO4Solution.
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| CN201710516704.8A CN107200383A (en) | 2017-06-29 | 2017-06-29 | A kind of method that selective light electrocatalytic oxidation removes Atrazine |
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| CN201710516704.8A CN107200383A (en) | 2017-06-29 | 2017-06-29 | A kind of method that selective light electrocatalytic oxidation removes Atrazine |
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| CN110947373A (en) * | 2019-11-14 | 2020-04-03 | 同济大学 | Photoelectric catalytic material for selectively removing phthalate pollutants by controlling pore diameter and treatment method |
| CN112978869A (en) * | 2021-03-17 | 2021-06-18 | 东莞理工学院 | Efficient selective Ti/SnO2Preparation method and application of (E) -Sb-MI anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110947373A (en) * | 2019-11-14 | 2020-04-03 | 同济大学 | Photoelectric catalytic material for selectively removing phthalate pollutants by controlling pore diameter and treatment method |
| CN112978869A (en) * | 2021-03-17 | 2021-06-18 | 东莞理工学院 | Efficient selective Ti/SnO2Preparation method and application of (E) -Sb-MI anode material |
| CN112978869B (en) * | 2021-03-17 | 2022-03-11 | 东莞理工学院 | Efficient selective Ti/SnO2Preparation method and application of (E) -Sb-MI anode material |
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