CN101555050A - Method for preparing BDD-TiO2 pole with P-N junction characteristic - Google Patents
Method for preparing BDD-TiO2 pole with P-N junction characteristic Download PDFInfo
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- CN101555050A CN101555050A CNA2008101035182A CN200810103518A CN101555050A CN 101555050 A CN101555050 A CN 101555050A CN A2008101035182 A CNA2008101035182 A CN A2008101035182A CN 200810103518 A CN200810103518 A CN 200810103518A CN 101555050 A CN101555050 A CN 101555050A
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Abstract
The invention prepares an N-TiO2/P-boron-doping diamond thin film (BDD)-TiO2 pole which has the P-N junction characteristics, can effectively process organic pollutants in water and belongs to the application field of water processing technologies. The BDD-TiO2 pole is prepared by a dipping, drawing and calcining method. The BDD pole surface appearance and the cover degree of TiO2 on the BDD pole surface are regulated and controlled by regulating experiment parameters, such as titanium dioxide sol concentration, pore-forming inducer concentration, drawing speed, calcination temperature, and the like. The synthesized BDD-TiO2 pole has the P-N junction characteristics. A prepared hybrid pole is used as a photoanode, photocoupling is carried out by applying certain applied voltage and ultra-violet light radiation and using the respective characteristics of photocatalysis and electro-oxidation technologies so as to catalyze and degrade the organic pollutants in the water, and the pole has the effective and stable characteristics. The pole has the high efficiency for processing the organic pollutants in the water, has simple operation and convenient management in practical use, has a wider application range in an organic pollutant concentration and is suitable for the small-scale decentralized waste and feed water processing.
Description
Technical field
The invention belongs to water treatment field.Relate to a kind of new and effective electrode preparation and the application in water treatment.Be particularly related to N-type TiO
2The BDD-TiO that/P-type boron-doped diamond (BDD) constitutes with P-N P-N junction characteristicPN
2Electrode, and adopt organic pollutant in this electrode efficiency light electrocatalysis degradation water.
Background technology
In recent years, high-level oxidation technology has become one of persistence toxic organic pollutant effective ways in the elimination water body.Compare with electrooxidation with independent photochemical catalysis, organic pollutant has shown obvious concerted catalysis effect in electrooxidation and the photocatalysis coupled technical finesse water, has clear superiority.Load on the 70%TiO on the titanium plate
2/ 30%RuO
2, the TiO of load platinum
2/ Ti electrode, and β-PbO
2The TiO that modifies
2Electrode and load on ZnWO on the conductive glass
4Electrode has been used as anode material, and demonstrates obvious concerted catalysis effect.The light anode is the core of photoelectrocatalysioxidization oxidization technology.The above-mentioned base material that adopts electrode only uses as substrate, does not have or have only very faint electrocatalysis decomposing organic pollutant activity.
Electrode materials is a key factor of decision processing efficiency in the electrochemical oxidation technology.Graphite Electrodes the earliest and the most commonly used is cheap, but physical strength and poor to the catalytic organism oxidation capacity, oxygen evolution potential and current efficiency are low.The PbO that last century, the nineties grew up
2And SnO
2Have high oxygen separated overpotential and good electrocatalysis characteristic at electrode, but shortcoming such as this type of electrode surface chemical ingredients and character instability, life-span are low, the easy inactivation of catalytic performance fails always better to be solved.Diamond electrode is the electrode materials of a kind of novelty of nearest people's development.Especially along with the continuous development of diamond technology of preparing and doping techniques, BDD successfully is deposited on the matrixes such as tantalum, titanium and silicon single crystal.The BDD electrode has the P-type semiconductor characteristic, has very wide electrochemical window and lower background current.In addition, it has higher physical strength and chemical stability.As anode material, the BDD electrode also is subjected to people in recent years day by day and pays close attention to aspect the organism in anode electrooxidation water.Although the BDD electrode has the catalytic activity of superior anodic oxidation degradable organic pollutant, but also exist the low and high problem of energy consumption of catalytic efficiency that electric anodizing technology is difficult to overcome self, and anode is in the shortcoming of the easy passivation of catalyzed degradation Persistent organic pollutants.Especially in the dyestuff and phenols organic pollutant of electric anodic oxidation treatment difficult degradation, organism and degraded intermediate product thereof are very easily at electric anode surface generation electric polymerization reaction, and passivated electrodes is difficult to further carry out oxidizing reaction.Therefore overcome the weakness of BDD electrode, the catalytic oxidation activity has important theory and practical significance to make it have efficiently.
Summary of the invention
The present invention seeks to prepare the BDD-TiO with P-N P-N junction characteristicPN of efficient stable
2Electrode further improves the electro catalytic activity and the TiO of BDD electrode
2Photoelectric catalytically active, the work-ing life of improving quantum yield and electrode.
The present invention is directed to the deficiency of organic pollutant method in photochemical catalysis and the catalytic oxidation degraded water body, established TiO
2New approaches with BDD electrode photoelectric coupling and catalyzing degradable organic pollutant.In conjunction with TiO
2Semiconductor light-catalyst and BDD electrode photochemical catalysis and high characteristics and the characteristic of semiconductor of electro catalytic activity separately prepared the BDD-TiO with P-N knot
2Electrode is by adding the pore-forming inductor, regulation and control electrode surface pattern and TiO
2Coverage at the BDD electrode surface.The electrode of preparation is assembled into typical dyestuff and phenols organic pollutant in the anode photoelectricity coupling and catalyzing treating water.The present invention has principle and technical novelty.
The present invention specifically comprises following content: electrode makes up preparation; Microtexture and photoelectrochemical behaviour characterize; Organic pollutant in the photoelectrocatalysis treating water.Preparation BDD-TiO
2Electrode is a core content, obtains the controlled BDD-TiO of pattern by the regulation and control correlation parameter
2Electrode.Analyzing electrode surface phase structure, surface topography, surface coverage.Research BDD-TiO
2The electrode sample photoelectrochemical behaviour.Carry out organic pollutant in photochemical catalysis, electrooxidation and the photoelectric catalysis degrading water, analyze contaminant degradation kinetics and salinity; Identify the intermediate product of target contaminant in different catalytic processs; The stability of electrode processing efficiency when investigating long-time running.The photoelectrocatalysis reaction unit is traditional photoelectric reacting device.The electrode of preparation is a working electrode, and platinum filament is a counter electrode, and saturated calomel electrode is a reference electrode.Choose azoic dyestuff Acid Orange II and 2, and 4-two chlorophenols (2,4-DCP) be process object.
BDD-TiO
2Electrode preparation method is specific as follows:
The BDD electrode has been bought and has been obtained, and cuts into required size.At first add washing composition with clear water and carry out ultrasonic cleaning, its ammoniacal liquor and hydrogen peroxide mixed solution of putting into the process dilution, heated about 30 minutes then, clean successively with clear water and dehydrated alcohol, room temperature is air-dry.The BDD electrode that cleaned is immersed in TiO
2In the colloidal sol, under given pace, lift plated film then, after the thin film low temperature oven dry, calcination processing at a certain temperature.By regulating precursor concentration, add the amount of pore former, the rate of pulling and number of times can obtain the electrode sample of different coverages and thickness.
1) TiO
2The collosol concentration scope is 10%, 15%, 20%, 30% (weight ratio);
2) pore former is a tensio-active agent, and molecular weight is 800; The amount of control pore former is 5%, 10%, 15%, 20% and 30%, weight ratio);
3) the pull rate scope is 2,4,6,10cm/min;
4) calcining temperature is 450,500 degree; Calcination time is 1,2 and 4 hour.
Photoelectric catalysis degrading organic pollutant reactive system and experimental arrangement are described below:
Apply different anodic bias by electrochemical workstation, adopt target compound change in concentration under the liquid-phase chromatographic analysis different condition, study its degradation rate; Adopt total organic carbon analyzer evaluating objects thing salinity.Adopt the gas chromatograph mass spectrometer method that the intermediate product that the processing target thing generates in reaction process is identified.
Description of drawings
Fig. 1 is the Raman spectrogram of preparation electrode;
Fig. 2 is electrode atomic power Electronic Speculum figure;
Fig. 3 is the electrode sem photograph;
Fig. 4 is electrode electro Chemical ac resistance analysis result;
Fig. 5 is the clearance curve .a over time of Acid Orange II under the different condition, directly photodissociation; B, photocatalytic degradation; C, electrochemical oxidation (1 volt); D, photoelectric catalysis degrading (1 volt); E, photoelectric catalysis degrading (2 volts) (the Acid Orange II starting point concentration is 20 mg/litre, 60 milliliters of reaction solns, 20W ultra violet lamp);
Fig. 6 is for adding different bias voltages to Acid Orange II clearance influence (the Acid Orange II starting point concentration is 20 mg/litre, 60 milliliters of reaction solns, the 20W UV illumination is penetrated)
Fig. 7 is under the different condition 2, and the 4-DCP clearance changes (the Acid Orange II starting point concentration is 20 mg/litre, 60 milliliters of reaction solns, 20W ultra violet lamp, 2.5 volts of applied voltages) with the reaction times
Fig. 8 is the liquid spectrum analysis of reaction soln in electrooxidation and the photoelectrocatalysioxidization oxidization process.
Adopt this preparation electrode to carry out photoelectrocatalysioxidization oxidization degraded Acid Orange II
Electrode materials with preparation is the light anode, carries out the photoelectric catalysis degrading experiment in homemade photo electrocatalysis reactor.The photo electrocatalysis reactor volume is 60 milliliters, and counter electrode is a platinum filament, and saturated calomel electrode is a reference, and electrochemical workstation is the CHI660B electrochemical workstation that Shanghai occasion China produces.The starting point concentration of Acid Orange II is 30 mg/litre.Light source is the UV-light of 20W, and predominant wavelength is in 250 nanometers.
As seen from Figure 5, Acid Orange II is at ultraviolet light irradiation, alive outside effect, and the degraded that under ultraviolet light irradiation and impressed voltage act on simultaneously, all obtains, and the speed maximum of degrading in photoelectric action, and along with the raising of impressed voltage, degradation rate increases (Fig. 6).The degradation rate that shows Acid Orange II in the photoelectric process by analysis is greater than independent photochemical catalysis electrooxidation effect sum, and photoelectricity has synergy.
Adopt this preparation electrode to carry out photoelectrocatalysioxidization oxidization and handle 2,4-DCP
Select 2,4-DCP is a process object, and aldehydes matter is a typical organic pollutant in the trade effluent.It is the light anode that embodiment 2 selects the electrode with preparation, carries out the photoelectric catalysis degrading experiment in homemade photo electrocatalysis reactor.The photo electrocatalysis reactor volume is 60 milliliters, and counter electrode is a platinum filament, and saturated calomel electrode is a reference, and electrochemical workstation is the CHI660B electrochemical workstation that Shanghai occasion China produces.2, the starting point concentration of 4-DCP is 30 mg/litre.Light source is the UV-light of 20W, and predominant wavelength is in 250 nanometers.
As seen from Figure 7,2,4-DCP can degrade in electrooxidation and the photoelectrocatalysioxidization oxidization process in photochemical catalytic oxidation, and in the photoelectrocatalysioxidization oxidization process 2, the degradation rate maximum of 4-DCP.As seen from Figure 8, in electro-oxidation process, along with 2, the reduction of 4-DCP peak value have intermediate product to generate, and the peak value of intermediate product raises along with the prolongation in reaction times.But in the photoelectrocatalysioxidization oxidization process, have intermediate product to generate in initial reaction stage, along with the prolongation in reaction times, the peak value of intermediate product reduces.Show that intermediate product also is degraded.
Claims (5)
1. the independent boron-doped diamond film of ratio (BDD) electrode or TiO
2The better hybrid electrode of Persistent organic pollutants usefulness in the membrane electrode degradation water, realization is removed and mineralising more fast to Persistent organic pollutants in the water, it is characterized in that electrode has P-N knot effect, efficiently organic pollutant in the photoelectricity concerted catalysis oxide treatment water.
2. one kind prepares the electrode that is used for removing the water organic pollutant as claimed in claim 1, it is characterized in that, the light anode that adopts collosol and gel and dipping to lift the technology preparation has the P-N P-N junction characteristicPN, utilizes P type characteristics and the TiO of BDD
2N type characteristics, prepare the electrode materials of P-N P-N junction characteristicPN, have the activity of organic pollutant in the photoelectrocatalysioxidization oxidization degradation water efficiently;
3. the described electrode preparation method of claim 2 is characterized in that, BDD electrode surface TiO
2The charge capacity of material and surface tissue, selected TiO in the time of can preparing by adjusting
2Collosol concentration adds the concentration of pore former, the electrode pull rate, and institute's coating number, calcination times etc. are controlled and are regulated;
4. a method of removing organic pollutant in the water is characterized in that, both can adopt this electrode to carry out photochemical catalytic oxidation and remove that organic pollutant also can carry out organic pollutant in the Electrooxidation degradation water in the water, and photoelectricity acts on simultaneously has collaborative removal effect;
5. the described a kind of method of removing organic pollutant in the water of claim 4, it is characterized in that this method can be removed the pollutent in the water efficiently, both can be used for wastewater treatment, can be used for again also can handling the source water that contains the lower concentration Persistent organic pollutants to water treatment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786026A (en) * | 2010-03-24 | 2010-07-28 | 吉林大学 | n-shaped titanium oxide nanotube/p-shaped diamond heterojunction photocatalytic material and preparation method |
| CN103771633A (en) * | 2012-10-23 | 2014-05-07 | 中国科学院广州地球化学研究所 | Electrolytic treatment technology for smelting organic pollutants in waste water through high-salinity rare earth wet method |
| CN104047019A (en) * | 2013-03-11 | 2014-09-17 | 同济大学 | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof |
| JP2019005709A (en) * | 2017-06-26 | 2019-01-17 | 学校法人東京理科大学 | Purification apparatus, purification method, carbon material manufacturing method and carbon material |
-
2008
- 2008-04-08 CN CNA2008101035182A patent/CN101555050A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786026A (en) * | 2010-03-24 | 2010-07-28 | 吉林大学 | n-shaped titanium oxide nanotube/p-shaped diamond heterojunction photocatalytic material and preparation method |
| CN101786026B (en) * | 2010-03-24 | 2011-07-20 | 吉林大学 | n-shaped titanium oxide nanotube/p-shaped diamond heterojunction photocatalytic material and preparation method |
| CN103771633A (en) * | 2012-10-23 | 2014-05-07 | 中国科学院广州地球化学研究所 | Electrolytic treatment technology for smelting organic pollutants in waste water through high-salinity rare earth wet method |
| CN104047019A (en) * | 2013-03-11 | 2014-09-17 | 同济大学 | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof |
| JP2019005709A (en) * | 2017-06-26 | 2019-01-17 | 学校法人東京理科大学 | Purification apparatus, purification method, carbon material manufacturing method and carbon material |
| JP7012951B2 (en) | 2017-06-26 | 2022-01-31 | 学校法人東京理科大学 | Purification equipment, purification method, carbon material manufacturing method and carbon material |
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Open date: 20091014 |