CN108675382A - One kind being based on TiO2The integrated catalytic system and its degradation process method of nano pipe light catalyst - Google Patents

One kind being based on TiO2The integrated catalytic system and its degradation process method of nano pipe light catalyst Download PDF

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Publication number
CN108675382A
CN108675382A CN201810408048.4A CN201810408048A CN108675382A CN 108675382 A CN108675382 A CN 108675382A CN 201810408048 A CN201810408048 A CN 201810408048A CN 108675382 A CN108675382 A CN 108675382A
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tio
nanotube
anode
catalytic system
nano pipe
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CN108675382B (en
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王竹梅
张天峰
左建林
李月明
沈宗洋
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Jingdezhen Ceramic Institute
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Jingdezhen Ceramic Institute
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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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • 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
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The invention discloses one kind being based on TiO2The integrated catalytic system of nano pipe light catalyst, including TiO2Nanotube, visible light source or sunlight, electrocatalysis device, oxygen charging pump；The electrocatalysis device is with TiO2Nanotube is anode, fiber graphite felt is cathode, and the anode, cathode are inserted into organic wastewater, and is connected respectively to the anode of regulated power supply, on cathode；The visible light source or sunlight correspondence are irradiated on anode；Fe is added in the organic wastewater2+, the oxygen charging pump is located at cathode.In addition it also discloses and is based on TiO using above-mentioned2The degradation process method of the integrated catalytic system of nano pipe light catalyst.The present invention passes through to TiO2Nanotube applies applying bias and forms external electric field environment, forms TiO2The combination of photocatalysis and electro-catalysis, and Fenton's reaction is further introduced, constitute TiO2The reaction of nanotube visible light catalytic, electrocatalytic reaction and Fenton's reaction are mutually coupled the integrated catalytic system of synergistic effect, to which the degradation efficiency to toxicity persistent organic pollutants be greatly improved.

Description

One kind being based on TiO2The integrated catalytic system and its degradation treatment of nano pipe light catalyst Method
Technical field
The present invention relates to technical field of waste water processing, more particularly to one kind being based on TiO2The integrated of nano pipe light catalyst is urged Change system and its degradation process method.
Background technology
High-level oxidation technology is the effective ways for handling waste water from dyestuff, and the mechanism of action of the technology is produced by different approaches The process of raw hydroxyl radical free radical (HO), HO once being formed, can induce a series of radical chain reaction, attack each in water Kind pollutant, until being degraded to carbon dioxide, water and other small molecule inorganic substances.Fenton is as the original of high-level oxidation technology Fe is illustrated in human hair2+/H2O2The thorough mineralizing and degrading of all organic matters almost can be that carbon dioxide and water etc. are inorganic by system, the system Small-molecule substance, reaction mechanism are as follows：
H++Fe2++H2O2→Fe3++HO·
TiO2Light-catalyzed reaction also belong to the advanced oxidation processes that can generate HO, semiconductor TiO2The meeting under the excitation of light Generate light induced electron and hole, wherein light induced electron has very strong reducing power, photohole to have very strong oxidability, can TiO will be adsorbed on2The OH on surfaceOr hydrone is oxidized to hydroxyl radical free radical (HO), and HO is exactly degradation of organic substances It is crucial.
However, only single TiO2Its degradation property of photocatalysis is not so good, and the prior art is by TiO2Light-catalyzed reaction and sweet smell Reaction is combined to improve catalytic treatment effect, but usually used is TiO2Nano-powder is unfavorable for recycling. Therefore, in recent years with TiO2Nano-tube array becomes research hotspot as catalysis material.But since light enters nanotube Loss of strength is serious afterwards, greatly reduces utilization rate of the pipe internal surface in catalysis, and because of TiO2Nano-tube array, which is grown in, leads In the titanium substrate of electricity, TiO2The light induced electron and hole generated under light excitation is also more prone to compound, thus quantum is imitated Rate is relatively low, and photocatalysis efficiency is also far from the requirement for reaching practical application；Also, since spectral response range is relatively narrow, TiO2 The energy gap of semiconductor is 3.2eV, can only generate response in 390nm ultraviolet lights below to wavelength, thus to sunlight Utilization rate is extremely low.
Therefore, currently available technology is for the big organic pollution difficult to degrade of organic pollution, especially toxicity, processing effect Fruit is bad, it is difficult to and reach efficient degradation, still needs to research and develop novel processing system and catalysis material, it is big to toxicity to effectively improve The degradation efficiency of persistent organic pollutants promotes the progress and development of wastewater processing technology.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind being based on TiO2The collection of nano pipe light catalyst At catalysis system, by TiO2Nanotube applies applying bias and forms external electric field environment, forms TiO2Photocatalysis and electro-catalysis In conjunction with further introducing Fenton's reaction in addition, constitute TiO2The reaction of nanotube visible light catalytic, electrocatalytic reaction and Fenton are anti- It should be mutually coupled the integrated catalytic system of synergistic effect, to increase substantially the effect of the degradation to toxicity persistent organic pollutants Rate.Another object of the present invention is to provide be based on TiO using above-mentioned2The degradation of the integrated catalytic system of nano pipe light catalyst Processing method.
The purpose of the present invention is achieved by the following technical programs：
It is provided by the invention a kind of based on TiO2The integrated catalytic system of nano pipe light catalyst, including TiO2Nanotube, can Light-exposed light source or sunlight, electrocatalysis device, oxygen charging pump；The electrocatalysis device is with TiO2Nanotube is anode, fibrous stone Black felt is cathode, and the anode, cathode be inserted into organic wastewater, and is connected respectively to the anode of regulated power supply, on cathode；Institute It states visible light source or sunlight correspondence is irradiated on anode；Fe is added in the organic wastewater2+, the oxygen charging pump is located at cloudy At pole.
Integrated catalytic system of the present invention, by TiO2Visible light catalytic reaction system, electrocatalytic reaction system and Fenton's reaction System combinations form.TiO2Visible light catalytic reaction system realizes degradation of organic waste water under visible light；Meanwhile by the two poles of the earth Between apply voltage, to TiO2Nanotube applies applying bias and forms external electric field environment；Fenton's reaction system is to have Fe is added in machine waste water2+While it being made of the quick-fried air of oxygen charging pump in cathode.
Further, Fe in organic wastewater of the present invention2+A concentration of 0.01~0.10mmol/L.
Further, TiO of the present invention2Nanotube is composite modified TiO2Nanotube, i.e. PdO load N, B codope two Titanium oxide nanotubes, wherein titanium dioxide exists with anatase-phase nano pipe array format；The palladium is loaded in the form of PdO In titania nanotube surface, the surface atom concentration of the palladium is 0.1~0.2%；The surface atom concentration of the nitrogen is 1.0~2.0%, the surface atom concentration of the boron is 0.3~0.5%.
In said program, composite modified TiO of the invention2Nanotube, the nitrogen-atoms enter the replacement of titanium dioxide lattice Oxygen atom forms O-Ti-N keys；The boron atom is adulterated in two forms, is respectively：B-O-Ti is formed into titanium dioxide lattice Key, surface atom concentration is 0.2~0.3%, with B2O3Form be carried on titania nanotube surface, surface atom A concentration of 0.1~0.2%.The titania nanotube is the nano-tube array being grown on Ti -- N alloy sheet matrix.
In said program, composite modified TiO of the invention2The preparation method of nanotube is to be made first with Ti -- N alloy piece Organic solution for anode, containing boron source is that electrolyte carries out electrochemical anodization reaction, and the Ti -- N alloy piece reaction generates N Adulterate TiO2While nano-tube array, B doping enters TiO2Nanotube, to which N, B codope titanium dioxide nanotube battle array be made Row；Then N, B codope titanium dioxide nanotube is impregnated in PdCl2In solution, make PdCl2It is adsorbed in nanotube surface； After through drying, calcining, obtain PdO load N, B codope titanium dioxide nanotube photochemical catalyst.
About the composite modified TiO of the present invention2The preparation method of nanotube can take following concrete measure, including following step Suddenly：
(1) preparation of Ti -- N alloy piece
It is prepared using the method for arc-melting-rapid cooling, titanium sponge is mixed with TiN powder first, is suppressed through hydraulic press At electrode block, it is placed in cold-mo(u)ld furnace and carries out melting as anode, obtain blocky Ti -- N alloy；Then by institute It states blocky Ti -- N alloy to be cut, polished, pre-processed, obtains Ti -- N alloy piece；
(2) preparation of N, B codope titanium dioxide nanotube
Using the Ti -- N alloy piece as anode, with dissolved with NaBF4、NH4The ethylene glycol of F and the mixed solution of water are as electricity It solves liquid and carries out electrochemical anodization reaction, relative to ethylene glycol, the NaBF4、NH4F, the dosage of water be respectively 0.4~ 0.8wt%, 0.2~0.5wt%, 5~15vol%；The anodic oxidation reactions time is 10~30h；Through washing after reaction completion It washs, dry, calcine, obtain N, B codope titanium dioxide nanotube；
(3) PdO loads the preparation of N, B codope titanium dioxide nanotube
It is 0.001~0.005mol/L's that N, B codope titanium dioxide nanotube, which is impregnated in palladium ion concentration, PdCl215~30h is impregnated in the mixed solution of ethyl alcohol and water, then through drying, calcining, obtains PdO load N, B codope two Titanium oxide nanotubes.
Further, the composite modified TiO of the present invention2The dosage of TiN powder is sea in step (1) described in nanometer tube preparation method 2~4mol% of continuous titanium.Calcination temperature is 450~550 DEG C in the step (2), and heating rate is 4 DEG C/min, soaking time For 1~2h；Calcination temperature is 400~500 DEG C in the preparation method step (3), and heating rate is 4 DEG C/min, soaking time For 1~2h.
Another object of the present invention is achieved by the following technical programs：
It is provided by the invention to be based on TiO using above-mentioned2The degradation treatment side of the integrated catalytic system of nano pipe light catalyst Method includes the following steps：
(1) FeSO is added in organic wastewater4·7H2O forms Fe2+A concentration of 0.01~0.10mmol/L's contains Fe2+Have Machine waste water, it is 5~7 to adjust its pH value；
(2) by the TiO2Nanotube is connected to as anode on the anode of regulated power supply, by porous fiber graphite felt It is connected on the cathode of regulated power supply as cathode, the anode, cathode, which are inserted into, contains Fe2+In organic wastewater, it is seen that radiant or Sunlight correspondence is irradiated on anode, and oxygen charging pump is located at exposure air at cathode, and aeration rate is 2~5L/min；Simultaneously in negative and positive Two interpolars apply 1~2V of voltage, and operating temperature is room temperature, and degradation time is 30~120min.
The invention has the advantages that：
(1) integrated catalytic system of the present invention, in TiO2On the basis of visible light catalytic reaction, by TiO2Nanotube is applied Add applying bias to form external electric field environment, to promote the separation of light induced electron and hole, solves TiO2Quantum efficiency is lower to ask Topic, forms TiO2The combination of photocatalysis and electro-catalysis；In addition Fenton's reaction is further introduced, to collect TiO2Visible light is urged Change reaction, electrocatalytic reaction and Fenton's reaction in one, three kinds of reactions are mutually coupled synergistic effect, are greatly improved to toxicity The degradation efficiency of persistent organic pollutants, can the other methods of efficient degradation organic pollution difficult to degrade, and nothing in system Chemical sludge generates, and processing cost is low, and treatment effeciency is high, is of great significance to wastewater processing technology.
(2) the required Fe of Fenton's reaction in the present invention2+It is to be added in waste water, the amount of addition is easily controllable；It is required Hydrogen peroxide is that (oxygen i.e. in the exposed air of oxygen charging pump, is adsorbed more soluble in waste water solution by cathode by exposing air generation In, dissolved oxygen and TiO under light illumination2The light induced electron on surface passes through series reaction, generates hydrogen peroxide), it is not only not necessarily to direct Hydrogen peroxide is added and has saved cost, and also eliminates solution stirring, reduces preparation process and equipment cost.
(3) the composite modified TiO that the present invention uses2Nano pipe light catalyst, TiO2Nanotube high-sequential is grown, and compares table Area is big.By the binary synergistic effect of the codoping modified generation of N, B, efficiently solve the problems, such as that spectral response range is narrow, Titania nanotube is set more effectively to absorb visible light；The load of PdO makes the photo-generate electron-hole of nanotube simultaneously To separative efficiency be improved significantly, PdO can not only capture photohole, PdO itself still good catalyst, to make Obtain TiO2With stronger photocatalytic activity.
(4) the composite modified TiO that the present invention uses2Under nano pipe light catalyst visible light catalytic activity it is high, it is safe and non-toxic, It is good to recycle facility, recycling performance, there is very high practical value and application prospect.
(5) operation of integrated catalytic system of the present invention is simple for process, and influence factor is easy to control, helps to promote and answer With.
Description of the drawings
Below in conjunction with embodiment and attached drawing, the present invention is described in further detail：
Fig. 1 is that the present invention is based on TiO2The integrated catalytic system principle schematic diagram of nano pipe light catalyst；
Fig. 2 (a) is N, B codope TiO in the embodiment of the present invention one2Scanning electron microscope (SEM) photo (times magnification of nanotube Number is 30000 times, and illustration amplification factor therein is 100000 times)；
Fig. 2 (b) is composite modified TiO obtained in the embodiment of the present invention one2The scanning electron microscope of nano pipe light catalyst (SEM) photo (amplification factor is 100000 times)；
Fig. 3 is composite modified TiO made from the unmodified titania nanotube of comparative example A and the embodiment of the present invention one2It receives The XRD spectrum of mitron photochemical catalyst；
Fig. 4 is composite modified TiO made from the embodiment of the present invention one2The XPS N1s of N are adulterated in nano pipe light catalyst Spectrum；
Fig. 5 is composite modified TiO made from the embodiment of the present invention one2The XPS B1s of B are adulterated in nano pipe light catalyst Spectrum；
Fig. 6 is composite modified TiO made from the embodiment of the present invention one2The XPS Pd3d of Pd are adulterated in nano pipe light catalyst Spectrum；
Fig. 7 be the embodiment of the present invention one to five, comparative example A, comparative example B degradation simulative organic wastewater organic total carbon (TOC) curve graph.
Specific implementation mode
TiO of the embodiment of the present invention2Nanotube is composite modified TiO2Nanotube, i.e. PdO load N, B codope titanium dioxide Nanotube, in its preparation process, with commercially available purity Ti >=99.7%, granularity be 3~10mm titanium sponge and granularity be 200, the TiN powder of purity TiN >=99.9% is that raw material prepares Ti -- N alloy piece.
Embodiment one：
1, the present embodiment is based on TiO2The integrated catalytic system of nano pipe light catalyst, as shown in Figure 1, including composite modified TiO2Nanotube, visible light source or sunlight, electrocatalysis device, oxygen charging pump.It builds and degradation process method is as follows：
(1) using the amaranth azo dyes of a concentration of 200mg/L as simulative organic wastewater, by 100mL organic wastewaters and FeSO4·7H2O is added in transparent reaction vessel and forms Fe2+The organic wastewater of a concentration of 0.03mmol/L, with hydrochloric acid or ammonium hydroxide tune It is 6 to save its pH value；
(2) electrocatalysis device is with composite modified TiO2Nanotube is anode, and porous fiber graphite felt, which is cut into, to be similar to TiO2As cathode, anode, cathode are inserted into above-mentioned containing Fe the strip of nanotube sample2+In organic wastewater, and it is connected respectively to On the anode of regulated power supply, cathode；Visible light source is using the 200W xenons for being mounted with ultraviolet light cut-off filter plate (λ >=400nm) Lamp, correspondence are irradiated on anode, and oxygen charging pump is located at exposure air, aeration rate 3L/min at cathode；Simultaneously in two interpolar of negative and positive Apply voltage 1V, operating temperature is room temperature, degradation time 30min.
2, the composite modified TiO in the present embodiment integrated catalytic system2Nanotube loads N, B codope titanium dioxide for PdO The step of titanium nanotube, preparation method, is as follows：
(1) preparation of Ti -- N alloy piece
It is prepared using the method for arc-melting-rapid cooling, is first the titanium sponge and TiN powder (TiN powder of 500g by total amount Dosage be titanium sponge 3mol%) mixing, be pressed into electrode block through hydraulic press, be placed in conduct in cold-mo(u)ld furnace Anode carries out melting, and smelting parameter is：Vacuum degree 2 × 10-2Pa, voltage 35V, electric current 250A, obtain blocky Ti -- N alloy；So Above-mentioned blocky Ti -- N alloy is cut afterwards, is polished, the Ti -- N alloy piece that size is 4cm × 1cm × 0.1cm is made；
Above-mentioned Ti -- N alloy piece is pre-processed：First use sand paper sanding and polishing to surface no marking, then successively into Row acetone sonochemistry oil removing and distilled water are cleaned by ultrasonic each 10min, (polishing fluid is in molar ratio HF: HNO to chemical polishing 10s3 =1: 1 mixed liquor), it is finally totally spare with distilled water flushing；
(2) preparation of N, B codope titanium dioxide nanotube
Electrochemical anodization reaction is carried out using D.C. regulated power supply, is sun with above-mentioned pretreated Ti -- N alloy piece Pole, platinized platinum are connected to as cathode in equipment, electrode spacing 2cm；With 30mL dissolved with NaBF4、NH4The ethylene glycol of F and mixing for water Solution is closed as electrolyte, relative to ethylene glycol, NaBF4、NH4F, the dosage of water is respectively 0.6wt%, 0.4wt%, 6vol%； Ti -- N alloy piece is inserted into 1cm, oxidation voltage 60V, oxidation time 20h under electrolyte；Reaction is washed after completing through ethyl alcohol It washs, after drying, calcined for 4 DEG C/min to 450 DEG C with heating rate at a temperature of 80 DEG C, keep the temperature 2h, obtain N, B codope Anatase type titanium dioxide nano tube, microscopic appearance are shown in that Fig. 2 (a), crystalline structure are shown in Fig. 3；
(3) PdO loads the preparation of N, B codope titanium dioxide nanotube
Above-mentioned N, B codope titanium dioxide nanotube is impregnated in the PdCl that palladium ion concentration is 0.003mol/L2Ethyl alcohol With the mixed solution (PdCl of water2Pure for commercially available analysis, the volume ratio of ethyl alcohol and water is 1: 1) in, 20h is impregnated, in 80 DEG C of temperature Then lower drying is warming up to 400 DEG C with 4 DEG C/min of heating rate and is calcined, keep the temperature 2h, obtains PdO load N, B codopes Titanic oxide nano pipe light catalyst, microscopic appearance are shown in that Fig. 2 (a), crystalline structure are shown in Fig. 3.
Comparative example A's (unmodified titania nanotube)：
It is comparative example A with unmodified titania nanotube, preparation method is as follows：Embodiment one the step of in (1), Ti -- N alloy piece is replaced by the metal titanium foil of 0.5mm by 99.5%, thickness with commercially available purity；Embodiment one the step of in (2), Electrolyte is free of NaBF4；Without one step of embodiment (3).Obtained unmodified titania nanotube, crystalline structure See Fig. 3.
Fig. 2 (a) shows that N, B codope titanium dioxide nanotube made from the present embodiment step (2) display high-sequential, Gap length of the nanometer bore between 70~110nm, thickness of pipe wall 15~50nm, Guan Yuguan is 0~100nm.
Fig. 2 (b) and Fig. 2 (a) are compared as it can be seen that PdO has successfully been loaded on N, B codope titanium dioxide nanotube, PdO Sedimentary particle is equably attached to nanotube nozzle while gap between having filled up Guan Yuguan, and part PdO deposits enter In nanotube, PdO sediment distributions are uniform, and grain size is tiny.
As seen from Figure 3, the crystalline structure of titania nanotube is rutile titania before and after N, B codope and before and after PdO loads Mine type.
As shown in figure 4, N1s combinations can be 401.78eV, N element enters TiO2Lattice forms O-Ti-N keys, surface atom A concentration of 1.21%.
As shown in figure 5, B1s combinations can enter TiO for the B of 192.26eV2Lattice, forms Ti-O-B keys, and surface atom is dense Degree is 0.22%；Existence form in conjunction with the B that can be 193.01eV is B2O3, surface atom concentration 0.13%.
As shown in fig. 6, Pd 3d5/2Photoelectron peak is made of 2 different acromions of intensity, in conjunction with can be respectively 336.34 And 341.72eV, it is 5.38eV that two peaks, which combine energy difference, and Pd elements are with Pd2+(PdO) form exists, Pd element surface atom concentrations It is 0.12%.
Embodiment two：
1, the present embodiment is based on TiO2The integrated catalytic system of nano pipe light catalyst exists with one difference of embodiment In：Using the tetrabromobisphenol A of a concentration of 20mg/L as simulative organic wastewater, it is 7, aeration rate 4L/min to adjust pH value, when degradation Between be 50min.
2, the composite modified TiO in the present embodiment integrated catalytic system2The preparation method of nanotube is different from embodiment one Place is：
In step (1), the dosage of TiN powder is the 3.5mol% of titanium sponge.
In step (2), the NaBF in electrolyte4Its dosage is 0.4wt%, oxidation time 30h.
Embodiment three：
1, the present embodiment is based on TiO2The integrated catalytic system of nano pipe light catalyst exists with one difference of embodiment In：Using the tetracycline of a concentration of 20mg/L as simulative organic wastewater, it is 7 to adjust pH value, aeration rate 4L/min, degradation time For 60min.
2, the composite modified TiO in the present embodiment integrated catalytic system2The preparation method of nanotube is different from embodiment one Place is：
In step (2), the NaBF in electrolyte4Its dosage is 0.4wt%.
In step (3), palladium ion concentration is 0.004mol/L in the mixed solution of dipping.
Example IV：
1, the present embodiment is based on TiO2The integrated catalytic system of nano pipe light catalyst exists with one difference of embodiment In：With 2, the 4- chlorophenesic acids of a concentration of 20mg/L for simulative organic wastewater, it is 5, aeration rate 4L/min, drop to adjust pH value The solution time is 60min.
2, the composite modified TiO in the present embodiment integrated catalytic system2The preparation method of nanotube is different from embodiment one Place is：
In step (1), the dosage of TiN powder is the 2.5mol% of titanium sponge.
In step (3), palladium ion concentration is 0.002mol/L, dip time 30h in the mixed solution of dipping.
Embodiment five：
1, the present embodiment is based on TiO2The integrated catalytic system of nano pipe light catalyst exists with one difference of embodiment In：Using the phenol of a concentration of 20mg/L as simulative organic wastewater, it is 5 to adjust pH value, aeration rate 4L/min, and degradation time is 60min。
2, the composite modified TiO in the present embodiment integrated catalytic system2The preparation method of nanotube is different from embodiment one Place is：
In step (2), the NaBF in electrolyte4Its dosage is 0.8wt%.
In step (3), dip time 30h.
Performance test：
In various embodiments of the present invention organic wastewater degraded processing procedure, taking appropriate organic wastewater to survey it every 10min has Machine total carbon (TOC), and calculate TOC/TOC0(TOC0, TOC be respectively to degrade forward and backward organic total carbon).
The unmodified titania nanotube of above-mentioned comparative example A is replaced into answering in one integrated catalytic system of the embodiment of the present invention Close modified TiO2Nanotube, degradation treatment is the same as embodiment one.
With one composite modified TiO of embodiment2Nanotube only carries out visible light catalytic reaction B (i.e. organic wastes as a comparison case FeSO is added without in water4·7H2O, without oxygen charging pump, to composite modified TiO2Nanotube does not apply voltage), degradation treatment is same Embodiment one.
Various embodiments of the present invention, comparative example A, test results are shown in figure 7 by comparative example B.
As seen from Figure 7, compared with comparative example A, the composite modified TiO of the embodiment of the present invention2Nano pipe light catalyst has Good visible light catalysis activity；Compared with comparative example B, integrated catalytic of embodiment of the present invention system is to amaranth azo dyes Degradation rate greatly improves；From the embodiment of the present invention two to five as it can be seen that toxic organic compound difficult to degrade such as tetrabromobisphenol A, Fourth Ring Element, 2,4- chlorophenesic acids, phenol, degradation efficiency are very high.

Claims (10)

1. one kind being based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：Including TiO2It is nanotube, visible Radiant or sunlight, electrocatalysis device, oxygen charging pump；The electrocatalysis device is with TiO2Nanotube is anode, fiber graphite Felt is cathode, and the anode, cathode are inserted into organic wastewater, and is connected respectively to the anode of regulated power supply, on cathode；It is described Visible light source or sunlight correspondence are irradiated on anode；Fe is added in the organic wastewater2+, the oxygen charging pump is located at cathode Place.
2. according to claim 1 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：It is described Fe in organic wastewater2+A concentration of 0.01~0.10mmol/L.
3. according to claim 1 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：It is described TiO2Nanotube is composite modified TiO2Nanotube, i.e. PdO load N, B codope titanium dioxide nanotube, wherein titanium dioxide Exist with anatase-phase nano pipe array format；The palladium is carried on titania nanotube surface, the palladium in the form of PdO Surface atom concentration be 0.1~0.2%；The surface atom concentration of the nitrogen is 1.0~2.0%, the surface atom of the boron A concentration of 0.3~0.5%.
4. according to claim 3 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：It is described Nitrogen-atoms enters titanium dioxide lattice and forms O-Ti-N keys instead of oxygen atom；The boron atom is adulterated in two forms, is respectively： B-O-Ti keys are formed into titanium dioxide lattice, surface atom concentration is 0.2~0.3%, with B2O3Form be carried on dioxy Change titanium nanotube surface, surface atom concentration is 0.1~0.2%.
5. according to claim 3 or 4 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：Institute It is the nano-tube array being grown on Ti -- N alloy sheet matrix to state titania nanotube.
6. according to claim 5 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：It is described Composite modified TiO2The preparation method of nanotube is that the organic solution first using Ti -- N alloy piece as anode, containing boron source is electricity It solves liquid and carries out electrochemical anodization reaction, the Ti -- N alloy piece reaction generates N and adulterates TiO2While nano-tube array, B Doping enters TiO2Nanotube, to which N, B codope titanium dioxide nanotube array be made；Then by N, B codope two Titanium oxide nanotubes are impregnated in PdCl2In solution, make PdCl2It is adsorbed in nanotube surface；After through drying, calcining, obtain PdO loads N, B codope titanium dioxide nanotube photochemical catalyst.
7. according to claim 6 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：It is described Composite modified TiO2The preparation method of nanotube includes the following steps：
(1) preparation of Ti -- N alloy piece
It is prepared using the method for arc-melting-rapid cooling, titanium sponge is mixed with TiN powder first, electricity is pressed into through hydraulic press Pole block is placed in cold-mo(u)ld furnace and carries out melting as anode, obtains blocky Ti -- N alloy；Then by described piece Shape Ti -- N alloy is cut, is polished, is pre-processed, and Ti -- N alloy piece is obtained；
(2) preparation of N, B codope titanium dioxide nanotube
Using the Ti -- N alloy piece as anode, with dissolved with NaBF4、NH4The ethylene glycol of F and the mixed solution of water are as electrolyte Carry out electrochemical anodization reaction, relative to ethylene glycol, the NaBF4、NH4F, the dosage of water be respectively 0.4~0.8wt%, 0.2~0.5wt%, 5~15vol%；The anodic oxidation reactions time is 10~30h；Washed, dry after the completion of reaction, Calcining, obtains N, B codope titanium dioxide nanotube；
(3) PdO loads the preparation of N, B codope titanium dioxide nanotube
N, B codope titanium dioxide nanotube is impregnated in the PdCl that palladium ion concentration is 0.001~0.005mol/L2Second 15~30h is impregnated in the mixed solution of alcohol and water, then through drying, calcining, obtains PdO load N, B codope titanium dioxides Nanotube.
8. according to claim 7 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：It is described The dosage of TiN powder is 2~4mol% of titanium sponge in preparation method step (1).
9. according to claim 7 be based on TiO2The integrated catalytic system of nano pipe light catalyst, it is characterised in that：It is described Calcination temperature is 450~550 DEG C in preparation method step (2), and heating rate is 4 DEG C/min, and soaking time is 1~2h；It is described Calcination temperature is 400~500 DEG C in preparation method step (3), and heating rate is 4 DEG C/min, and soaking time is 1~2h.
10. using TiO is based on described in one of claim 1-92The degradation treatment side of the integrated catalytic system of nano pipe light catalyst Method, it is characterised in that include the following steps：
(1) FeSO is added in organic wastewater4·7H2O forms Fe2+A concentration of 0.01~0.10mmol/L's contains Fe2+Organic waste Water, it is 5~7 to adjust its pH value；
(2) by the TiO2Nanotube is connected to as anode on the anode of regulated power supply, using porous fiber graphite felt as the moon Pole is connected on the cathode of regulated power supply, and the anode, cathode, which are inserted into, contains Fe2+In organic wastewater, it is seen that radiant or sunlight Correspondence is irradiated on anode, and oxygen charging pump is located at exposure air at cathode, and aeration rate is 2~5L/min；Simultaneously in two interpolar of negative and positive Apply 1~2V of voltage, operating temperature is room temperature, and degradation time is 30~120min.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113248057A (en) * 2021-04-29 2021-08-13 濮阳天地人环保科技股份有限公司 Method for treating shallow bubble gas production wastewater by virtue of electrochemistry and sodium hypochlorite
CN113321353A (en) * 2021-04-23 2021-08-31 大唐环境产业集团股份有限公司 Photoelectrocatalysis wastewater treatment system and treatment method
CN113526646A (en) * 2021-08-20 2021-10-22 中南大学 electro-Fenton system for in-situ production of hydrogen peroxide by cathode/anode and application of electro-Fenton system in strengthening degradation of organic pollutants
CN114162911A (en) * 2021-10-29 2022-03-11 南京师范大学 Gd (Gd)3+With Ti3+Co-doped TiO2Nanotube array electrode, preparation method and application thereof
CN114956251A (en) * 2022-04-28 2022-08-30 常州大学 Self-electrically-driven hydrogen peroxide oxidation coupling photocatalytic degradation treatment process and system

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101947459A (en) * 2010-10-14 2011-01-19 华中师范大学 Visible light active boron nitrogen codope titanium dioxide hollow sphere catalyst and preparation method thereof
CN103446699A (en) * 2013-09-06 2013-12-18 广西大学 Method for cooperatively degrading organic matters by visible light photoelectric-Fenton
CN103449563A (en) * 2013-09-06 2013-12-18 广西大学 Method for removing organic matter under synergy of visible light photoelectric catalysis and three-dimensional electrode/electro-fenton
CN103964563A (en) * 2014-05-23 2014-08-06 广西大学 Visible-light photoelectric-Fenton method for efficiently degrading organic substances
KR101466914B1 (en) * 2014-06-19 2014-12-04 한양대학교 산학협력단 Method for Manufacturing Titanium Dioxide Nanotube Photocatalyst and water treatment apparatus Using the Same
CN106299418A (en) * 2016-08-16 2017-01-04 上海交通大学 The photocatalysis wastewater fuel cell, manufacture of strengthening radical reaction and preparation method and application
CN106395976A (en) * 2016-11-05 2017-02-15 北京飞纳环保科技有限公司 Method and device for treating organophosphorus pesticide wastewater by virtue of photoelectrochemistry synergy based on titanium dioxide nanotube array

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101947459A (en) * 2010-10-14 2011-01-19 华中师范大学 Visible light active boron nitrogen codope titanium dioxide hollow sphere catalyst and preparation method thereof
CN103446699A (en) * 2013-09-06 2013-12-18 广西大学 Method for cooperatively degrading organic matters by visible light photoelectric-Fenton
CN103449563A (en) * 2013-09-06 2013-12-18 广西大学 Method for removing organic matter under synergy of visible light photoelectric catalysis and three-dimensional electrode/electro-fenton
CN103964563A (en) * 2014-05-23 2014-08-06 广西大学 Visible-light photoelectric-Fenton method for efficiently degrading organic substances
KR101466914B1 (en) * 2014-06-19 2014-12-04 한양대학교 산학협력단 Method for Manufacturing Titanium Dioxide Nanotube Photocatalyst and water treatment apparatus Using the Same
CN106299418A (en) * 2016-08-16 2017-01-04 上海交通大学 The photocatalysis wastewater fuel cell, manufacture of strengthening radical reaction and preparation method and application
CN106395976A (en) * 2016-11-05 2017-02-15 北京飞纳环保科技有限公司 Method and device for treating organophosphorus pesticide wastewater by virtue of photoelectrochemistry synergy based on titanium dioxide nanotube array

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
RATNAWATI LI ET AL.,: "Effect of NaBF4 addition on the anodic synthesis of TiO2 nanotube arrays photocatalyst for production of hydrogen from glycerol-water solution", 《NTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
XIAOJING HU ET AL.,: "Highly photostable palladium一loaded Ti02 nanotubes and the active species in the photodegradation of methyl orange", 《催化学报》 *
王光辉: "《分子识别作用下环境内分泌干扰物光降解及机制》", 31 March 2011, 中国环境科学出版社 *
王竹梅等: "添加NaBF4对阳极氧化法制备TiO2纳米管光催化剂的影响", 《无机化学学报》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321353A (en) * 2021-04-23 2021-08-31 大唐环境产业集团股份有限公司 Photoelectrocatalysis wastewater treatment system and treatment method
CN113321353B (en) * 2021-04-23 2022-04-26 大唐环境产业集团股份有限公司 Photoelectrocatalysis wastewater treatment system and treatment method
CN113248057A (en) * 2021-04-29 2021-08-13 濮阳天地人环保科技股份有限公司 Method for treating shallow bubble gas production wastewater by virtue of electrochemistry and sodium hypochlorite
CN113526646A (en) * 2021-08-20 2021-10-22 中南大学 electro-Fenton system for in-situ production of hydrogen peroxide by cathode/anode and application of electro-Fenton system in strengthening degradation of organic pollutants
CN113526646B (en) * 2021-08-20 2022-04-05 中南大学 electro-Fenton system for in-situ production of hydrogen peroxide by cathode/anode and application of electro-Fenton system in strengthening degradation of organic pollutants
CN114162911A (en) * 2021-10-29 2022-03-11 南京师范大学 Gd (Gd)3+With Ti3+Co-doped TiO2Nanotube array electrode, preparation method and application thereof
CN114162911B (en) * 2021-10-29 2023-05-02 南京师范大学 Gd (Gd) type drug delivery device 3+ With Ti 3+ Co-doped TiO 2 Nanotube array electrode, preparation method and application thereof
CN114956251A (en) * 2022-04-28 2022-08-30 常州大学 Self-electrically-driven hydrogen peroxide oxidation coupling photocatalytic degradation treatment process and system

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