CN108675382B - Based on TiO2Integrated catalytic system of nanotube photocatalyst and degradation treatment method thereof - Google Patents
Based on TiO2Integrated catalytic system of nanotube photocatalyst and degradation treatment method thereof Download PDFInfo
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Abstract
The invention discloses a method based on TiO2Integrated catalytic system of nanotube photocatalyst comprising TiO2Nanotube, visible light source or sunlight, electric catalytic unit, and oxygen pump; the electrocatalytic device is made of TiO2The nanotube is an anode, the fibrous graphite felt is a cathode, and the anode and the cathode are both inserted into the organic wastewater and are respectively connected to the anode and the cathode of the voltage-stabilized power supply; the visible light source or the sunlight correspondingly irradiates the anode; fe is added into the organic wastewater2+The oxygenation pump is located at the cathode. In addition, the use of the above TiO-based material is also disclosed2A degradation treatment method of an integrated catalytic system of a nanotube photocatalyst. The invention is through to TiO2Applying external bias to the nanotube to form an external electric field environment to form TiO2The combination of photocatalysis and electrocatalysis, and further introduces Fenton reaction to form TiO2The integrated catalytic system with the synergistic effect of the mutual coupling of the visible light catalytic reaction, the electrocatalytic reaction and the Fenton reaction of the nanotube greatly improves the degradation efficiency of toxic refractory organic pollutants.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method based on TiO2An integrated catalytic system of a nanotube photocatalyst and a degradation treatment method thereof.
Background
Advanced oxidation technology is an effective method for treating dye wastewater, and the action mechanism of the technology is a process for generating hydroxyl radicals (HO) through different ways, and once HO is formed, a series of free radical chain reactions are induced to attack various pollutants in water until the pollutants are degraded into carbon dioxide, water and other small-molecule inorganic substances. Fenton as an advanced oxidation technologyThe founder of the surgery invented Fe2+/H2O2The system can almost completely mineralize and degrade all organic matters into inorganic micromolecular substances such as carbon dioxide, water and the like, and the reaction mechanism is as follows:
H++Fe2++H2O2→Fe3++HO·
TiO2also belongs to the advanced oxidation method capable of generating HO & lt- & gt, semiconductor TiO2Under the excitation of light, photo-generated electrons and holes can be generated, wherein the photo-generated electrons have strong reducing capability, and the photo-generated holes have strong oxidizing capability, so that the photo-generated holes can be adsorbed on TiO2OH of the surface－Or the water molecules are oxidized into hydroxyl radicals (HO), and HO is the key for degrading organic matters.
However, only a single TiO2The degradation performance of the photocatalysis is not good, and the prior art uses TiO2Photocatalytic reaction and Fenton reaction are combined to improve catalytic treatment effect, but TiO is generally used2Nano-powder, which is not conducive to recycling. Therefore, in recent years TiO has been used2Nanotube arrays have become a focus of research as photocatalytic materials. However, the loss of intensity is serious after the light enters the nanotube, so that the utilization rate of the inner surface of the tube in catalysis is greatly reduced, and the TiO is used for the purpose of reducing the loss of the intensity of the light2The nanotube array is grown on a conductive metallic titanium substrate, TiO2The photoproduction electrons and holes generated under the light excitation are easier to be combined, so that the quantum efficiency is lower, and the photocatalytic efficiency of the photogeneration electrons and holes can not meet the requirement of practical application; furthermore, TiO has a narrow spectral response range2The semiconductor has a forbidden band width of 3.2eV, and can respond only to ultraviolet light having a wavelength of 390nm or less, and thus the utilization rate of sunlight is extremely low.
Therefore, in the prior art, the treatment effect of organic pollutants, especially organic pollutants with high toxicity and difficult degradation, is not good, and efficient degradation is difficult to achieve, and a novel treatment system and a novel catalytic material still need to be developed to effectively improve the degradation efficiency of organic pollutants with high toxicity and difficult degradation and promote the progress and development of a wastewater treatment technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a TiO-based material2Integrated catalytic system of nanotube photocatalyst by reacting with TiO2Applying external bias to the nanotube to form an external electric field environment to form TiO2The combination of photocatalysis and electrocatalysis, and furthermore, Fenton reaction is introduced to form TiO2The integrated catalytic system with the synergistic effect of the visible light catalytic reaction, the electrocatalytic reaction and the Fenton reaction of the nanotube is mutually coupled, so that the degradation efficiency of toxic refractory organic pollutants is greatly improved. Another object of the present invention is to provide a method for producing a titanium oxide film using the above TiO-based2A degradation treatment method of an integrated catalytic system of a nanotube photocatalyst.
The purpose of the invention is realized by the following technical scheme:
the invention provides a TiO-based material2Integrated catalytic system of nanotube photocatalyst comprising TiO2Nanotube, visible light source or sunlight, electric catalytic unit, and oxygen pump; the electrocatalytic device is made of TiO2The nanotube is an anode, the fibrous graphite felt is a cathode, and the anode and the cathode are both inserted into the organic wastewater and are respectively connected to the anode and the cathode of the voltage-stabilized power supply; the visible light source or the sunlight correspondingly irradiates the anode; fe is added into the organic wastewater2+The oxygenation pump is located at the cathode.
The invention relates to an integrated catalytic system consisting of TiO2The visible light catalytic reaction system, the electrocatalytic reaction system and the Fenton reaction system. TiO 22The visible light catalytic reaction system realizes the degradation of organic wastewater under visible light; at the same time, a voltage is applied between the two electrodes to apply a voltage to the TiO2Applying an external bias to the nanotube to form an external electric field environment; the Fenton reaction system is to add Fe into organic wastewater2+And meanwhile, the cathode is formed by oxygen-charging pump explosion air.
Further, Fe in the organic wastewater of the invention2+The concentration of (b) is 0.01-0.10 mmol/L.
Further, the TiO of the present invention2The nanotube is a composite materialTiO 22The nanotube is a PdO loaded N, B co-doped titanium dioxide nanotube, wherein the titanium dioxide exists in an anatase phase nanotube array form; the palladium is loaded on the surface of the titanium dioxide nanotube in a PdO form, and the surface atomic concentration of the palladium is 0.1-0.2%; the surface atomic concentration of nitrogen is 1.0-2.0%, and the surface atomic concentration of boron is 0.3-0.5%.
In the scheme, the composite modified TiO of the invention2The nitrogen atoms enter titanium dioxide crystal lattices to replace oxygen atoms to form O-Ti-N bonds; the boron atoms are doped in two forms, respectively: enters titanium dioxide crystal lattices to form a B-O-Ti bond, the surface atomic concentration of the B-O-Ti bond is 0.2-0.3 percent, and B is used2O3The surface of the titanium dioxide nanotube is loaded in the form of (1) and the surface atomic concentration of the titanium dioxide nanotube is 0.1-0.2%. The titanium dioxide nanotube is a nanotube array grown on a Ti-N alloy sheet substrate.
In the scheme, the composite modified TiO of the invention2The preparation method of the nanotube comprises the steps of firstly, taking a Ti-N alloy sheet as an anode and taking organic solution containing a boron source as electrolyte to carry out electrochemical anodic oxidation reaction, wherein the Ti-N alloy sheet is reacted to generate N-doped TiO2While nanotube arrays, B doping into TiO2Preparing N, B co-doped titanium dioxide nanotube array; then the N, B codoped titanium dioxide nanotube is dipped in PdCl2In solution, PdCl is added2Adsorbing on the surface of the nanotube; and then drying and calcining to obtain the PdO loaded N, B co-doped titanium dioxide nanotube photocatalyst.
The invention relates to composite modified TiO2The preparation method of the nanotube can adopt the following specific measures, and comprises the following steps:
(1) preparation of Ti-N alloy sheet
The preparation method is characterized by adopting an electric arc melting-rapid cooling method, firstly mixing titanium sponge and TiN powder, pressing the mixture into an electrode block by an oil press, and putting the electrode block into a consumable electrode vacuum electric arc furnace to be used as an anode for smelting to obtain a blocky Ti-N alloy; then cutting, polishing and pretreating the blocky Ti-N alloy to obtain a Ti-N alloy sheet;
(2) n, B preparation of co-doped titanium dioxide nanotube
Using the Ti-N alloy sheet as an anode to dissolve NaBF4、NH4Using the mixed solution of ethylene glycol and water of F as electrolyte to carry out electrochemical anodic oxidation reaction, and relative to ethylene glycol, the NaBF is4、NH4F. The amount of water is 0.4-0.8 wt%, 0.2-0.5 wt%, 5-15 vol%; the anodic oxidation reaction time is 10-30 h; after the reaction is finished, washing, drying and calcining to obtain N, B co-doped titanium dioxide nanotubes;
(3) preparation of PdO loaded N, B co-doped titanium dioxide nanotube
Soaking the N, B co-doped titanium dioxide nanotube in PdCl with palladium ion concentration of 0.001-0.005 mol/L2Soaking the mixed solution of ethanol and water for 15-30 h, and then drying and calcining to obtain the PdO loaded N, B co-doped titanium dioxide nanotube.
Further, the composite modified TiO of the invention2The usage amount of TiN powder in the step (1) of the nanotube preparation method is 2-4 mol% of the titanium sponge. In the step (2), the calcining temperature is 450-550 ℃, the heating rate is 4 ℃/min, and the heat preservation time is 1-2 h; in the preparation method, in the step (3), the calcination temperature is 400-500 ℃, the heating rate is 4 ℃/min, and the heat preservation time is 1-2 h.
The other purpose of the invention is realized by the following technical scheme:
the invention provides the use of the above TiO-based2The degradation treatment method of the integrated catalytic system of the nanotube photocatalyst comprises the following steps:
(1) adding FeSO into organic wastewater4·7H2O to Fe2+Fe-containing alloy with a concentration of 0.01 to 0.10mmol/L2+Adjusting the pH value of the organic wastewater to 5-7;
(2) subjecting the TiO to a reaction2The nanotube is connected to the positive electrode of a regulated power supply as the anode, the porous fibrous graphite felt is connected to the negative electrode of the regulated power supply as the cathode, and the anode and the cathode are inserted with Fe2+Visible light in organic wastewaterCorrespondingly irradiating the anode by a light source or sunlight, and exposing air at the cathode by an oxygen filling pump at an aeration rate of 2-5L/min; meanwhile, a voltage of 1-2V is applied between the cathode and the anode, the working temperature is room temperature, and the degradation time is 30-120 min.
The invention has the following beneficial effects:
(1) the invention integrates a catalytic system in TiO2On the basis of visible light catalytic reaction, by reacting on TiO2The nanotube is applied with external bias to form an external electric field environment to promote the separation of photo-generated electrons and holes and solve the problem of TiO2The problem of low quantum efficiency, the formation of TiO2A combination of photocatalysis and electrocatalysis; furthermore, a Fenton reaction is further introduced, so that TiO is collected2Visible light catalytic reaction, electrocatalytic reaction and Fenton reaction are integrated, the three reactions are mutually coupled and act synergistically, the degradation efficiency of toxic refractory organic pollutants is greatly improved, organic pollutants refractory to other methods can be efficiently degraded, no chemical sludge is generated in a system, the treatment cost is low, the treatment efficiency is high, and the method has important significance on a wastewater treatment technology.
(2) Fe required for Fenton reaction in the present invention2+The additive is added into the wastewater, and the adding amount is easy to control; the necessary hydrogen peroxide is generated by air exposure (namely oxygen in the air exposed by the oxygen charging pump is absorbed by a cathode and is more easily dissolved in the wastewater solution, and the oxygen and TiO are dissolved under the illumination2The photo-generated electrons on the surface generate hydrogen peroxide through a series of reactions), so that the cost is saved by not directly adding hydrogen peroxide, the solution stirring is also saved, and the preparation steps and the equipment cost are reduced.
(3) The composite modified TiO adopted by the invention2Nanotube photocatalyst, TiO2The nanotubes grow in high order and have large specific surface area. The problem of narrow spectral response range is effectively solved through a binary synergistic effect generated by the co-doping modification of N, B, so that the titanium dioxide nanotube can absorb visible light more effectively; meanwhile, the separation efficiency of the photo-generated electron-hole pairs of the nanotube is obviously improved by the PdO load, the PdO not only can capture the photo-generated holes, but also is a good catalyst, so that the PdO is used as a catalystTo obtain TiO2Has stronger photocatalytic activity.
(4) The composite modified TiO adopted by the invention2The nano-tube photocatalyst has high catalytic activity under visible light, is safe and nontoxic, is convenient to recycle, has good recycling performance, and has high practical value and application prospect.
(5) The integrated catalytic system has simple operation process, easily controlled influence factors and contribution to popularization and application.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
FIG. 1 is a diagram of the present invention based on TiO2Schematic diagram of integrated catalytic system of nanotube photocatalyst;
FIG. 2(a) shows N, B codoped TiO2Scanning Electron Microscope (SEM) images of nanotubes (30000 x magnification, where inset is 100000 x magnification);
FIG. 2(b) is the composite modified TiO prepared in the first embodiment of the present invention2Scanning Electron Microscope (SEM) pictures (magnification 100000 times) of nanotube photocatalysts;
FIG. 3 shows the unmodified TiO nanotube of comparative example A and the modified TiO composition obtained in the first embodiment of the present invention2XRD pattern of nanotube photocatalyst;
FIG. 4 shows a modified TiO compound prepared in accordance with the first embodiment of the present invention2XPS N1s spectra of N doped nanotubes in the photocatalyst;
FIG. 5 shows a modified TiO compound prepared in accordance with the first embodiment of the present invention2XPS B1s spectra of B doped nanotubes in the photocatalyst;
FIG. 6 shows a modified TiO compound prepared in accordance with the first embodiment of the present invention2XPS Pd3d spectra of Pd doped in nanotube photocatalyst;
FIG. 7 is a graph of Total Organic Carbon (TOC) of simulated organic wastewater from the degradation of examples one to five, comparative example A and comparative example B of the present invention.
Detailed Description
Example TiO of the invention2The nano tube is composite modified TiO2In the preparation process of the nanotube, namely the PdO loaded N, B co-doped titanium dioxide nanotube, a Ti-N alloy sheet is prepared by using commercially available titanium sponge with the purity of more than or equal to 99.7 percent and the granularity of 3-10 mm and TiN powder with the granularity of 200 and the purity of more than or equal to 99.9 percent as raw materials.
The first embodiment is as follows:
1. this example is based on TiO2An integrated catalytic system of nanotube photocatalyst, as shown in FIG. 1, comprises composite modified TiO2Nanotube, visible light source or sunlight, electric catalytic unit, and oxygen pump. The construction and degradation treatment method comprises the following steps:
(1) using amaranth azo dye with the concentration of 200mg/L as simulated organic wastewater, and mixing 100mL of organic wastewater and FeSO4·7H2Adding O into a transparent reaction vessel to form Fe2+Adjusting the pH value of the organic wastewater with the concentration of 0.03mmol/L to 6 by using hydrochloric acid or ammonia water;
(2) electrocatalysis device for composite modification of TiO2The nanotube is used as anode, and porous fibrous graphite felt is cut into similar TiO2The strip of the nanotube sample is used as a cathode, and the anode and the cathode are inserted into the Fe-containing material2+The organic wastewater is respectively connected to the anode and the cathode of a stabilized voltage power supply; the visible light source adopts a 200W xenon lamp provided with an ultraviolet light cut-off filter (lambda is more than or equal to 400nm), the visible light source correspondingly irradiates the anode, the oxygen charging pump is positioned at the cathode to expose air, and the aeration rate is 3L/min; meanwhile, a voltage of 1V is applied between the cathode and the anode, the working temperature is room temperature, and the degradation time is 30 min.
2. Composite modified TiO in the Integrated catalytic System of this example2The nanotube is a PdO loaded N, B co-doped titanium dioxide nanotube, and the preparation method comprises the following steps:
(1) preparation of Ti-N alloy sheet
The preparation method is characterized in that an electric arc melting-rapid cooling method is adopted, firstly, 500g of sponge titanium and TiN powder (the amount of TiN powder is 3mol percent of the sponge titanium) are mixed, pressed into an electrode block by an oil press, and placed in a consumable electrode vacuum electric arc furnace to be used as an anode for smelting, wherein the smelting parameters are as follows: degree of vacuum of 2X 10-2Pa, voltage 35V and current 250A to obtain a blockA Ti-N alloy; then cutting and polishing the blocky Ti-N alloy to prepare a Ti-N alloy sheet with the size of 4cm multiplied by 1cm multiplied by 0.1 cm;
pretreating the Ti-N alloy sheet: firstly, using sand paper to polish and polish the surface until no scratch is left, then sequentially carrying out acetone ultrasonic chemical degreasing and distilled water ultrasonic cleaning for 10min and chemical polishing for 10s respectively (the polishing solution is HF: HNO according to the mol ratio)3Mixed solution with the ratio of 1: 1), and finally, washing the mixture by using distilled water for later use;
(2) n, B preparation of co-doped titanium dioxide nanotube
Adopting a direct current stabilized power supply to carry out electrochemical anodic oxidation reaction, taking the pretreated Ti-N alloy sheet as an anode and a platinum sheet as a cathode to be connected to equipment, wherein the electrode distance is 2 cm; 30mL of NaBF dissolved in4、NH4A mixed solution of ethylene glycol and water of F is used as an electrolyte, and NaBF is relative to ethylene glycol4、NH4F. The amount of water is 0.6 wt%, 0.4 wt% and 6 vol% respectively; inserting the Ti-N alloy sheet into the electrolyte for 1cm, wherein the oxidation voltage is 60V, and the oxidation reaction time is 20 h; after the reaction is finished, washing with ethanol, drying at the temperature of 80 ℃, calcining at the heating rate of 4 ℃/min to 450 ℃, and preserving heat for 2h to obtain N, B co-doped anatase titanium dioxide nanotubes, wherein the microscopic morphology of the nanotubes is shown in figure 2(a), and the crystal structure of the nanotubes is shown in figure 3;
(3) preparation of PdO loaded N, B co-doped titanium dioxide nanotube
Soaking the N, B codoped titanium dioxide nanotube in PdCl with palladium ion concentration of 0.003mol/L2Mixed solution of ethanol and water (PdCl)2The volume ratio of ethanol to water is 1: 1), soaking for 20h, drying at 80 ℃, then heating to 400 ℃ at a heating rate of 4 ℃/min, calcining, and preserving heat for 2h to obtain the PdO loaded N, B co-doped titanium dioxide nanotube photocatalyst, wherein the microstructure of the photocatalyst is shown in figure 2(a), and the crystal structure of the photocatalyst is shown in figure 3.
Comparative example a (unmodified titania nanotubes):
the preparation method of the unmodified titanium dioxide nanotube used as the comparative example A is as follows: in step (1) of example one, the product is listed in marketSelling a metal titanium foil with the purity of 99.5 percent and the thickness of 0.5mm to replace the Ti-N alloy sheet; in step (2) of example one, the electrolyte contained no NaBF4(ii) a Example one, step (3), was not performed. The crystal structure of the prepared unmodified titanium dioxide nanotube is shown in figure 3.
Fig. 2(a) shows that the N, B co-doped titanium dioxide nanotubes prepared in step (2) of this embodiment are highly ordered, the inner diameter of the nanotube is 70-110 nm, the wall thickness of the tube is 15-50 nm, and the width of the gap between the tubes is 0-100 nm.
As can be seen from comparison between fig. 2(b) and fig. 2(a), PdO is successfully loaded on N, B co-doped titanium dioxide nanotubes, PdO deposit particles are uniformly attached to the nanotube openings while filling gaps between the tubes, and part of PdO deposits enter the nanotubes, and the PdO deposits are uniformly distributed and have fine particle sizes.
As can be seen from fig. 3, the crystal structures of the titanium dioxide nanotubes before and after N, B co-doping and before and after PdO loading are anatase.
As shown in FIG. 4, the binding energy of N1s is 401.78eV, and N element enters TiO2The crystal lattice forms O-Ti-N bonds, and the surface atomic concentration is 1.21%.
As shown in FIG. 5, B1s with binding energy of 192.26eV for B into TiO2Crystal lattice, which forms Ti-O-B bond and has surface atomic concentration of 0.22%; b with a binding energy of 193.01eV is present in the form of B2O3The surface atomic concentration was 0.13%.
Pd3d as shown in FIG. 65/2The photoelectron peak consists of 2 shoulders with different intensities, the binding energy is 336.34 eV and 341.72eV, the difference between the binding energy of the two peaks is 5.38eV, and Pd is used as Pd element2+The (PdO) form exists, and the surface atomic concentration of Pd element is 0.12%.
Example two:
1. this example is based on TiO2The integrated catalytic system of the nanotube photocatalyst is different from the first embodiment in that: tetrabromobisphenol A with the concentration of 20mg/L is taken as simulated organic wastewater, the pH value is adjusted to 7, the aeration rate is 4L/min, and the degradation time is 50 min.
2. Recombination in the Integrated catalytic System of this exampleTiO 22The preparation method of the nanotube is different from the first embodiment in that:
in the step (1), the amount of TiN powder is 3.5 mol% of the titanium sponge.
In the step (2), NaBF in the electrolyte4The dosage of the catalyst is 0.4 wt%, and the oxidation reaction time is 30 h.
Example three:
1. this example is based on TiO2The integrated catalytic system of the nanotube photocatalyst is different from the first embodiment in that: tetracycline with the concentration of 20mg/L is used as simulated organic wastewater, the pH value is adjusted to 7, the aeration rate is 4L/min, and the degradation time is 60 min.
2. Composite modified TiO in the Integrated catalytic System of this example2The preparation method of the nanotube is different from the first embodiment in that:
in the step (2), NaBF in the electrolyte4The amount used was 0.4% by weight.
In the step (3), the concentration of palladium ions in the impregnated mixed solution is 0.004 mol/L.
Example four:
1. this example is based on TiO2The integrated catalytic system of the nanotube photocatalyst is different from the first embodiment in that: 2, 4-dichlorophenol with the concentration of 20mg/L is used as simulated organic wastewater, the pH value is adjusted to be 5, the aeration rate is 4L/min, and the degradation time is 60 min.
2. Composite modified TiO in the Integrated catalytic System of this example2The preparation method of the nanotube is different from the first embodiment in that:
in the step (1), the amount of TiN powder is 2.5 mol% of the titanium sponge.
In the step (3), the concentration of palladium ions in the impregnated mixed solution is 0.002mol/L, and the impregnation time is 30 h.
Example five:
1. this example is based on TiO2The integrated catalytic system of the nanotube photocatalyst is different from the first embodiment in that: phenol with the concentration of 20mg/L is used as simulated organic wastewater, the pH value is adjusted to 5, the aeration rate is 4L/min, and the degradation time is 60 min.
2. Composite modified TiO in the Integrated catalytic System of this example2The preparation method of the nanotube is different from the first embodiment in that:
in the step (2), NaBF in the electrolyte4The amount used was 0.8 wt%.
In the step (3), the dipping time is 30 h.
And (3) performance testing:
in the organic wastewater degradation treatment process of each embodiment of the invention, a proper amount of organic wastewater is taken every 10min to measure the Total Organic Carbon (TOC) of the wastewater, and the TOC/TOC is calculated0(TOC0And TOC is the total organic carbon before and after degradation, respectively).
The unmodified titanium dioxide nanotube of the comparative example A replaces the composite modified TiO in the integrated catalytic system of the embodiment of the invention2The degradation treatment of the nanotubes was the same as in example one.
Example one composite modified TiO2The nanotubes were subjected to visible light only catalytic reaction as comparative example B (i.e., no FeSO was added to the organic wastewater)4·7H2O, without oxygen pump, compound modified TiO2The nanotubes are not applied with voltage), and the degradation process is the same as in example one.
The test results of the examples of the present invention, comparative example a, and comparative example B are shown in fig. 7.
As can be seen from FIG. 7, the composite modified TiO of the examples of the present invention is compared with that of comparative example A2The nanotube photocatalyst has good visible light catalytic activity; compared with the comparative example B, the degradation rate of the integrated catalytic system of the embodiment of the invention to the amaranth azo dye is greatly improved; as can be seen from the second to fifth embodiments of the present invention, the degradation efficiency of refractory toxic organic compounds such as tetrabromobisphenol A, tetracycline, 2, 4-dichlorophenol and phenol is very high.
Claims (6)
1. Based on TiO2An integrated catalytic system of nanotube photocatalysts, characterized in that: comprising TiO2Nanotube, visible light source or sunlight, electric catalytic unit, and oxygen pump; the electrocatalytic device is made of TiO2The nanotube isThe anode and the fibrous graphite felt are used as cathodes, the anode and the cathode are inserted into the organic wastewater and are respectively connected to the anode and the cathode of a voltage-stabilized power supply, and the voltage applied between the anode and the cathode is 1-2V; the visible light source or the sunlight correspondingly irradiates the anode; fe is added into the organic wastewater2+Fe in organic waste water2+The concentration of the organic wastewater is 0.01-0.03 mmol/L, and the pH value of the organic wastewater is 5-7; the oxygen charging pump is positioned at the cathode;
the TiO is2The nano tube is composite modified TiO2The nanotube is a PdO loaded N, B co-doped titanium dioxide nanotube, wherein the titanium dioxide exists in the form of an anatase phase nanotube array and is a nanotube array grown on a Ti-N alloy sheet substrate; the palladium is loaded on the surface of the titanium dioxide nanotube in a PdO form, and the surface atomic concentration of the palladium is 0.1-0.2%; the surface atomic concentration of nitrogen is 1.0-2.0%, and the surface atomic concentration of boron is 0.3-0.5%; the nitrogen atoms enter titanium dioxide crystal lattices to replace oxygen atoms to form O-Ti-N bonds; the boron atoms are doped in two forms, respectively: enters titanium dioxide crystal lattices to form a B-O-Ti bond, the surface atomic concentration of the B-O-Ti bond is 0.2-0.3 percent, and B is used2O3The surface of the titanium dioxide nanotube is loaded in the form of (1) and the surface atomic concentration of the titanium dioxide nanotube is 0.1-0.2%.
2. The TiO-based according to claim 12An integrated catalytic system of nanotube photocatalysts, characterized in that: the composite modified TiO2The preparation method of the nanotube comprises the steps of firstly, taking a Ti-N alloy sheet as an anode and taking organic solution containing a boron source as electrolyte to carry out electrochemical anodic oxidation reaction, wherein the Ti-N alloy sheet is reacted to generate N-doped TiO2While nanotube arrays, B doping into TiO2Preparing N, B co-doped titanium dioxide nanotube array; then the N, B codoped titanium dioxide nanotube is dipped in PdCl2In solution, PdCl is added2Adsorbing on the surface of the nanotube; and then drying and calcining to obtain the PdO loaded N, B co-doped titanium dioxide nanotube photocatalyst.
3. The TiO-based according to claim 22An integrated catalytic system of nanotube photocatalysts, characterized in that: the composite modified TiO2The preparation method of the nanotube comprises the following steps:
(1) preparation of Ti-N alloy sheet
The preparation method is characterized by adopting an electric arc melting-rapid cooling method, firstly mixing titanium sponge and TiN powder, pressing the mixture into an electrode block by an oil press, and putting the electrode block into a consumable electrode vacuum electric arc furnace to be used as an anode for smelting to obtain a blocky Ti-N alloy; then cutting, polishing and pretreating the blocky Ti-N alloy to obtain a Ti-N alloy sheet;
(2) n, B preparation of co-doped titanium dioxide nanotube
Using the Ti-N alloy sheet as an anode to dissolve NaBF4、NH4Using the mixed solution of ethylene glycol and water of F as electrolyte to carry out electrochemical anodic oxidation reaction, and relative to ethylene glycol, the NaBF is4、NH4F. The amount of water is 0.4-0.8 wt%, 0.2-0.5 wt%, 5-15 vol%; the anodic oxidation reaction time is 10-30 h; after the reaction is finished, washing, drying and calcining to obtain N, B co-doped titanium dioxide nanotubes;
(3) preparation of PdO loaded N, B co-doped titanium dioxide nanotube
Soaking the N, B co-doped titanium dioxide nanotube in PdCl with palladium ion concentration of 0.001-0.005 mol/L2Soaking the mixed solution of ethanol and water for 15-30 h, and then drying and calcining to obtain the PdO loaded N, B co-doped titanium dioxide nanotube.
4. TiO-based according to claim 32An integrated catalytic system of nanotube photocatalysts, characterized in that: in the preparation method, in the step (1), the using amount of the TiN powder is 2-4 mol% of the titanium sponge.
5. TiO-based according to claim 32An integrated catalytic system of nanotube photocatalysts, characterized in that: in the preparation method, in the step (2), the calcination temperature is 450-550 DEG CThe heating rate is 4 ℃/min, and the heat preservation time is 1-2 h; in the preparation method, in the step (3), the calcination temperature is 400-500 ℃, the heating rate is 4 ℃/min, and the heat preservation time is 1-2 h.
6. Use of the TiO-based material according to one of claims 1 to 52The degradation treatment method of the integrated catalytic system of the nanotube photocatalyst is characterized by comprising the following steps of:
(1) adding FeSO into organic wastewater4·7H2O to Fe2+Fe-containing material with a concentration of 0.01 to 0.03mmol/L2+Adjusting the pH value of the organic wastewater to 5-7;
(2) subjecting the TiO to a reaction2The nanotube is connected to the positive electrode of a regulated power supply as the anode, the porous fibrous graphite felt is connected to the negative electrode of the regulated power supply as the cathode, and the anode and the cathode are inserted with Fe2+In the organic wastewater, a visible light source or sunlight correspondingly irradiates an anode, an oxygen charging pump is positioned at a cathode to expose air, and the aeration rate is 2-5L/min; meanwhile, a voltage of 1-2V is applied between the cathode and the anode, the working temperature is room temperature, and the degradation time is 30-120 min.
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