CN113603181B - Method for degrading oxytetracycline by double-chamber photoelectrocatalysis - Google Patents
Method for degrading oxytetracycline by double-chamber photoelectrocatalysis Download PDFInfo
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Abstract
The invention discloses a method for degrading terramycin by double-chamber photoelectrocatalysis, which comprises the specific steps of constructing a double-chamber photoelectrocatalysis system, degrading terramycin by the photoelectrocatalysis system under a xenon lamp, wherein: the graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode is prepared by a one-step method, and the high-efficiency degradation of terramycin is realized by the mode, so that the invention constructs a photoelectrocatalysis system with good stability, high photocatalytic activity, green and pollution-free properties and visible light photocatalytic activity.
Description
Technical Field
The invention relates to the field of pollutant photoelectrocatalysis, in particular to a method for degrading terramycin by double-chamber photoelectrocatalysis.
Background
In recent years, semiconductor-based photocatalytic technology has received attention because of its excellent characteristics in degrading organic pollutants.
Compared with a single photocatalysis process, the double-chamber photocatalysis process has lower energy consumption and higher degradation efficiency in the photo-anode chamber. At the same time, the removal of contaminants can also be achieved in the cathode chamber. The application of bias voltage in the process of photocatalysis can prevent the recombination of photo-generated electron-hole pairs, and the photocatalysis efficiency is remarkably improved. The double-chamber photoelectrocatalytic reaction system realizes the simultaneous degradation of terramycin, the generation of hydrogen and the reduction of carbon dioxide.
The degradation process of terramycin mainly comprises a biological treatment method, a chlorination method and a high-grade oxidation technology, wherein the high-grade oxidation technology has higher efficiency and is mainly divided into an ozone method, a Fenton method, a photodecomposition method, semiconductor treatment, a photoelectric treatment method and the like. The double-chamber photoelectrocatalysis treatment designed by the invention belongs to an advanced oxidation method, has high degradation efficiency compared with the prior art, and can realize synchronous degradation of terramycin in a light environment and a dark environment.
In the double-chamber photoelectrocatalysis system, the research on the degradation mechanism of terramycin has not been found. The electron gain and loss in the photo-anode and cathode compartments of the dual compartment photoelectrocatalysis system are different, so the degradation mechanism and action mechanism of oxytetracycline in the illuminated anode compartment and the dark ambient cathode compartment may be different. Therefore, the method for degrading the oxytetracycline by simulating the double-chamber photoelectrocatalysis system under the sunlight has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for degrading terramycin by double-chamber photoelectrocatalysis, which constructs a double-chamber photoelectrocatalysis system, applies graphite-phase carbon nitride to a titanium dioxide nanotube array photoelectrode to the double-chamber photoelectrocatalysis system, realizes synchronous degradation of terramycin on a cathode and an anode, and has the advantages of low price, good stability, high photoelectric conversion efficiency, high photocatalytic activity, greenness, no pollution and visible light photocatalytic activity.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method for degrading terramycin by double-chamber photoelectrocatalysis comprises the following specific steps:
s1: construction of double-chamber photoelectrocatalysis System
Connecting two quartz reactors with communicating pipes at the bottoms, adding a cation exchange membrane in the middle, respectively using self-made titanium dioxide nanotube array photoelectrodes doped with graphite phase carbon nitride as an anode and a cathode of a photoelectrocatalysis system, switching on the anode and the cathode, and irradiating the anode by using a xenon lamp;
s2, degrading terramycin by using photoelectric catalytic system
Adding a terramycin solution with a certain concentration into a reactor of the double-chamber photoelectrocatalysis system, turning on a xenon lamp, adjusting an external bias voltage, and degrading terramycin;
the graphite phase carbon nitride doped titanium dioxide nanotube array photoelectrode is prepared by adopting a one-step method, and the specific method is as follows: in a graphite-phase carbon nitride, anhydrous sodium sulfate and sodium fluoride mixed system solution, a pretreated titanium sheet is used as an anode, a platinum sheet is used as a cathode, and after anodic oxidation under a certain voltage condition, the oxidized titanium sheet anode is placed in a muffle furnace for high-temperature annealing, so that the self-made graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode is obtained.
Preferably, in the step S1, the power supply for connecting the anode and the cathode is a direct current stabilized voltage power supply, the distance between the xenon lamp and the anode reactor is 1-3cm, and the power of the xenon lamp is 100-150W.
Preferably, the concentration of oxytetracycline in the reactor in step S2 is 10-50mg/L, the xenon lamp is turned on simultaneously with an externally applied bias in the range of 0.5-1.5V, and the reaction temperature is 15-30 ℃.
Preferably, the titanium content in the titanium sheet is more than 99.9%, and the pretreatment method of the titanium sheet is as follows: washing off the surface oxide layer by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and cleaning the polished titanium sheet by using a cleaning agent.
Preferably, the cleaning agent is one or more of ethanol, acetone and deionized water.
Preferably, the preparation method of the graphite phase carbon nitride comprises the following steps: calcining melamine at 400-550 ℃, naturally cooling to room temperature after calcining, and grinding and crushing to obtain graphite-phase carbon nitride.
Preferably, the precursor of the graphite-phase carbon nitride in step S2 includes one or both of melamine and urea.
Preferably, the anodic oxidation voltage of the titanium sheet is 15-30V, the annealing temperature of the muffle furnace is 450-600 ℃, and the annealing time is 1-6h.
Preferably, the mixed solution system is prepared from graphite phase carbon nitride with the concentration of 0.2-1g/L, anhydrous sodium sulfate with the concentration of 0.5-1mol/L and sodium fluoride solution with the concentration of 0.2-0.6wt%, and the solution is prepared at present.
The invention has the beneficial effects that:
1. the invention constructs an effective double-chamber photoelectrocatalysis system for degrading terramycin, realizes synchronous degradation of terramycin on a cathode and an anode, prepares the titanium dioxide nanotube array photoelectrode with good electrode stability, high photoelectric conversion efficiency, high photocatalytic activity, green and pollution-free performance and visible light photocatalytic activity, and realizes efficient degradation of terramycin by applying the photoelectrode to the double-chamber photoelectrocatalysis system.
2. Compared with the traditional single-chamber photocatalysis technology, the double-chamber photocatalysis system can realize the degradation of terramycin in both light environment and dark environment. Under the same energy consumption, the degradation efficiency of the cathode is improved by 60%, and the combination of photocatalysis and electrocatalysis is utilized to generate superoxide radicals and hydroxyl radicals so as to complete the degradation of terramycin.
3. The invention is based on an anodic oxidation synchronous deposition process, graphite-phase carbon nitride is doped on the titanium dioxide nanotube array photoelectrode while being generated by a one-step method, the conduction band of the graphite carbon nitride is-1.1 eV, and the conduction band of the titanium dioxide is-0.29 eV. When the two are compounded, the excited electrons generated in the graphite carbon nitride conduction band can be transferred to the titanium dioxide conduction band, so that the separation of photo-generated carriers and holes is promoted, and more electron holes are generated to degrade pollutants; compared with the traditional process, namely the synthesis of the titanium dioxide nanotube array photoelectrode doped with the graphite phase carbon nitride is divided into two processes of the synthesis of the titanium dioxide nanotube array photoelectrode and the doping of the graphite phase carbon nitride, the preparation process is shortened, the problem of high preparation cost is solved, the preparation process steps are saved, and the photocatalytic performance is also improved.
4. Graphite carbon nitride, i.e. g-C 3 N 4 (4) The semiconductor has narrower band gap, can absorb visible light, and TiO 2 And g-C 3 N 4 The two energy levels are matched in position, heterojunction can be formed between the two energy levels during illumination, and photo-generated carriers are effectively separated, so that the method is an effective method for widening the light absorption range of the photo-generated carriers and promoting charge separation.
5. Compared with the graphite phase carbon nitride doped titanium dioxide nanotube array photoelectrode prepared by the traditional method, the photoelectric polarity prepared by the invention is more stable and has good recycling performance. The high degradation efficiency can be still maintained after five cycles. The titanium dioxide and the carbon nitride have synergistic effect, the titanium dioxide can be excited by light of ultraviolet band, the carbon nitride can be excited by light of visible band, and the utilization ratio of illumination is greatly improved.
Drawings
FIG. 1 is a comparison of the degradation effect of the present invention with anodes of three control groups that were photocatalytic alone, electrocatalytic alone, and unbiased;
FIG. 2 is a comparison of the degradation effect of the cathode of the present invention with three control groups of photocatalytic alone, electrocatalytic alone, unbiased;
FIG. 3 is a graph showing the effect of the anode and cathode on the degradation of oxytetracycline at various voltages in accordance with the present invention;
FIG. 4 is a graph showing the effect of the anode and cathode on the degradation of oxytetracycline at different pH's in accordance with the present invention;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode by one-step method
(1) Washing off a surface oxide layer of the titanium sheet by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and washing the polished titanium sheet by using ethanol, acetone and deionized water;
(2) Preparation of graphite-phase carbon nitride
Calcining melamine at 400-550 ℃, cooling to room temperature, and grinding and crushing to obtain graphite-phase carbon nitride;
(3) Preparing a mixed solution system with the concentration of graphite-phase carbon nitride of 0.2-1g/L, the concentration of anhydrous sodium sulfate of 0.5-1mol/L and the concentration of sodium fluoride of 0.2-0.6wt%, taking the titanium sheet treated in the step (1) as an anode, taking the platinum sheet as a cathode, carrying out anodic oxidation for 2-4h under the voltage condition of 15-30V, and then placing the anode in a muffle furnace for annealing for 1-6h at the temperature of 450-600 ℃ so as to obtain the graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode.
Two-chamber photoelectrocatalysis is utilized to degrade terramycin:
s1: construction of double-chamber photoelectrocatalysis System
The method comprises the steps of connecting two quartz reactors with the diameter of 3cm and the height of 10cm and a communicating pipe at the bottom, adding a cation exchange membrane in the middle, respectively using prepared graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrodes as an anode and a cathode of a photoelectrocatalysis system, connecting the anode and the cathode with a power supply, irradiating the anode with a 100-150W xenon lamp, and enabling the distance between the xenon lamp and the anode reactor to be 1-3cm.
S2: photocatalysed system for degrading terramycin under xenon lamp
The terramycin solution with the concentration of 10-50mg/L is added into a reactor of the double-chamber photoelectrocatalysis system, a xenon lamp is turned on, the external bias voltage is adjusted to be 0.5-1.5V, the terramycin is degraded at the reaction temperature of 15-30 ℃, and the concentration and degradation efficiency of the terramycin are calculated by using the absorbance of an ultraviolet-visible spectrophotometer at the wavelength of 356 nm.
Example 2
Preparation of graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode by one-step method
(1) Washing off a surface oxide layer of the titanium sheet by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and washing the polished titanium sheet by using ethanol, acetone and deionized water;
(2) Preparation of graphite-phase carbon nitride
Calcining melamine at 550 ℃, cooling to room temperature, and grinding and crushing to obtain graphite-phase carbon nitride;
(4) Preparing a mixed solution system with the concentration of graphite-phase carbon nitride of 1g/L, the concentration of anhydrous sodium sulfate of 0.5mol/L and the concentration of sodium fluoride of 0.2wt%, taking the titanium sheet treated in the step (1) as an anode, taking the platinum sheet as a cathode, carrying out anodic oxidation for 2h under the voltage condition of 15V, and then placing the anode in a muffle furnace for annealing at 450 ℃ for 1-6h, thereby obtaining the graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode.
Two-chamber photoelectrocatalysis for degrading terramycin
S1: construction of double-chamber photoelectrocatalysis System
The two quartz reactors with the diameter of 3cm and the height of 10cm and the bottom provided with a communicating pipe are connected, a cation exchange membrane is added in the middle, the prepared graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode is respectively used as an anode and a cathode of a photoelectrocatalysis system, the anode and the cathode are powered on, the anode is irradiated by a 150W xenon lamp, and the distance between the xenon lamp and the anode reactor is 3cm.
S2: photocatalysed system for degrading terramycin under xenon lamp
The terramycin solution with the concentration of 10mg/L is added into a reactor of the double-chamber photoelectrocatalysis system, a xenon lamp is turned on, the external bias voltage is adjusted to be 1.5V, the terramycin is degraded at the reaction temperature of 30 ℃, and the concentration and the degradation efficiency of the terramycin are calculated by using the absorbance of an ultraviolet-visible spectrophotometer at the wavelength of 356 nm.
Example 4
Preparation of graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode by one-step method
(1) Washing off a surface oxide layer of the titanium sheet by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and washing the polished titanium sheet by using ethanol, acetone and deionized water;
(2) Preparation of graphite-phase carbon nitride
Calcining melamine at 400 ℃, cooling to room temperature, and grinding and crushing to obtain graphite-phase carbon nitride;
(5) Preparing a mixed solution system with the concentration of graphite-phase carbon nitride of 0.5g/L, the concentration of anhydrous sodium sulfate of 1mol/L and the concentration of sodium fluoride of 0.6wt%, taking the titanium sheet treated in the step (1) as an anode, taking the platinum sheet as a cathode, carrying out anodic oxidation for 2h under the voltage condition of 30V, and then placing in a muffle furnace for annealing for 5h at the temperature of 450 ℃ so as to obtain the graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode.
Two-chamber photoelectrocatalysis for degrading terramycin
S1: construction of double-chamber photoelectrocatalysis System
The two quartz reactors with the diameter of 3cm and the height of 10cm and the bottom provided with a communicating pipe are connected, a cation exchange membrane is added in the middle, the prepared graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode is respectively used as an anode and a cathode of a photoelectrocatalysis system, the anode and the cathode are powered on, the anode is irradiated by a 100W xenon lamp, and the distance between the xenon lamp and the anode reactor is 2cm.
S2: photocatalysed system for degrading terramycin under xenon lamp
The terramycin solution with the concentration of 10mg/L is added into a reactor of the double-chamber photoelectrocatalysis system, a xenon lamp is turned on, the external bias voltage is adjusted to be 1V, the terramycin is degraded at the reaction temperature of 25 ℃, and the concentration and the degradation efficiency of the terramycin are calculated by using the absorbance of an ultraviolet-visible spectrophotometer at the wavelength of 356 nm.
Comparative example 1
Degradation of oxytetracycline by graphite-phase carbon nitride doped titanium dioxide nanotube array electrodes under single photocatalysis:
(1) Washing off a surface oxide layer of the titanium sheet by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and washing the polished titanium sheet by using ethanol, acetone and deionized water;
(2) Preparation of graphite-phase carbon nitride
Calcining melamine at 400 ℃, cooling to room temperature, and grinding and crushing to obtain graphite-phase carbon nitride;
(6) Preparing a mixed solution system with the concentration of graphite-phase carbon nitride of 0.5g/L, the concentration of anhydrous sodium sulfate of 1mol/L and the concentration of sodium fluoride of 0.6wt%, taking the titanium sheet treated in the step (1) as an anode, taking the platinum sheet as a cathode, carrying out anodic oxidation for 2h under the voltage condition of 30V, and then placing in a muffle furnace for annealing for 5h at the temperature of 450 ℃ so as to obtain the graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode.
Degradation of oxytetracycline using dual-chamber photocatalysis
S1: construction of a double-Chamber photocatalytic System
The two quartz reactors with the diameter of 3cm and the height of 10cm and the bottom provided with a communicating pipe are connected, a cation exchange membrane is added in the middle, the prepared graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode is respectively used as an anode and a cathode of a photoelectrocatalysis system, the anode is irradiated by a 100W xenon lamp, and the distance between the xenon lamp and the anode reactor is 2cm.
S2: photocatalytic system for degrading terramycin under xenon lamp
The terramycin solution with the concentration of 10mg/L is added into a reactor of the double-chamber photocatalysis system, a xenon lamp is turned on, the terramycin is degraded at the reaction temperature of 25 ℃, and the concentration and degradation efficiency of the terramycin are calculated by using the absorbance of an ultraviolet-visible spectrophotometer at the wavelength of 356 nm.
Comparative example 2
Degradation of oxytetracycline by graphite-phase carbon nitride doped titanium dioxide nanotube array electrodes under single electrocatalysis
(1) Washing off a surface oxide layer of the titanium sheet by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and washing the polished titanium sheet by using ethanol, acetone and deionized water;
(2) Preparation of graphite-phase carbon nitride
Calcining melamine at 400 ℃, cooling to room temperature, and grinding and crushing to obtain graphite-phase carbon nitride;
(7) Preparing a mixed solution system with the concentration of graphite-phase carbon nitride of 0.2g/L, the concentration of anhydrous sodium sulfate of 1mol/L and the concentration of sodium fluoride of 0.6wt%, taking the titanium sheet treated in the step (1) as an anode, taking the platinum sheet as a cathode, carrying out anodic oxidation for 2h under the voltage condition of 30V, and then placing in a muffle furnace for annealing for 6h at the temperature of 500 ℃ so as to obtain the graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode.
Two-chamber electrocatalytic degradation of oxytetracycline
S1: construction of a two-compartment electrocatalytic System
The two quartz reactors with the diameter of 3cm and the height of 10cm and the bottom provided with communicating pipes are connected, a cation exchange membrane is added in the middle, the prepared graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrodes are respectively used as an anode and a cathode of an electrocatalytic system, and the anode and the cathode are connected with a power supply.
S2: electro-catalytic system for degrading terramycin under xenon lamp
The terramycin solution with the concentration of 10mg/L is added into a reactor of the double-chamber photoelectrocatalysis system, the external bias voltage is adjusted to be 1V, the terramycin is degraded at the reaction temperature of 25 ℃, and the concentration and the degradation efficiency of the terramycin are calculated by using the absorbance of an ultraviolet-visible spectrophotometer at the wavelength of 356 nm.
Comparative example 2
Degradation of oxytetracycline by graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode under photoelectrocatalysis without external bias
Preparation of graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode by one-step method
(1) Washing off a surface oxide layer of the titanium sheet by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and washing the polished titanium sheet by using ethanol, acetone and deionized water;
(2) Preparation of graphite-phase carbon nitride
Calcining melamine at 400 ℃, cooling to room temperature, and grinding and crushing to obtain graphite-phase carbon nitride;
(8) Preparing a mixed solution system with the concentration of graphite-phase carbon nitride of 0.2g/L, the concentration of anhydrous sodium sulfate of 1mol/L and the concentration of sodium fluoride of 0.6wt%, taking the titanium sheet treated in the step (1) as an anode, taking the platinum sheet as a cathode, carrying out anodic oxidation for 2h under the voltage condition of 30V, and then placing in a muffle furnace for annealing for 6h at the temperature of 500 ℃ so as to obtain the graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode.
Two-chamber photoelectrocatalysis for degrading terramycin
S1: construction of double-chamber photoelectrocatalysis System
The method comprises the steps of connecting two quartz reactors with the diameter of 3cm and the height of 10cm and a communicating pipe at the bottom, adding a cation exchange membrane in the middle, respectively using prepared graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrodes as an anode and a cathode of a photoelectrocatalysis system, connecting the anode and the cathode by a wire, irradiating the anode by a 150W xenon lamp, and enabling the distance between the xenon lamp and the anode reactor to be 3cm.
S2: photocatalysed system for degrading terramycin under xenon lamp
The terramycin solution with the concentration of 10mg/L is added into a reactor of the double-chamber photoelectrocatalysis system, a xenon lamp is turned on, the terramycin is degraded at the reaction temperature of 25 ℃, and the concentration and degradation efficiency of the terramycin are calculated by using the absorbance of an ultraviolet-visible spectrophotometer at the wavelength of 356 nm.
From comparison of comparative examples 1-3 with the effect of the dual-chamber photoelectrocatalytic system on oxytetracycline, it can be seen from FIGS. 1-2 (E stands for electrocatalyst alone, P stands for photocatalysis alone, PW stands for electrocatalyst without externally applied bias, PE stands for dual-chamber photoelectrocatalysis of the present invention) that the degradation effect of the cathode is improved by 40% compared to comparative example 1; compared with comparative example 2, the degradation effect of the anode is improved by 80%, and the degradation effect of the cathode is improved by 60%; compared with comparative example 3, the degradation effect of the cathode is improved by 40%. The degradation effect is obvious, the degradation efficiency of the invention is highest, the degradation efficiency of the anode is up to 80% in 60min, the degradation efficiency of the cathode is 60%, and the synchronous degradation of terramycin in light environment and dark environment is realized. Under the combined action of photo-generated electrons and externally applied bias voltage in the light environment and the dark environment, the separation efficiency of photo-generated holes and electrons is improved, more hydroxyl free radicals and superoxide free radicals are generated, and the efficient degradation of terramycin is realized. Compared with other processes, the degradation effect is obviously improved.
As can be seen from fig. 3-4, the difference of the degradation effects of the double-chamber photoelectrocatalysis system on terramycin under different PH and different voltage is larger, and the degradation of terramycin is more favorable in alkaline environment, and the main acting species are hydroxyl free radicals and superoxide free radicals. The degradation effect of the cathode is greatly improved when the external bias voltage is positive, because the external power supply can promote the separation of photo-generated electrons and holes and inhibit the recombination of electron hole pairs when the external bias voltage is positive, thereby improving the degradation efficiency.
In conclusion, the invention constructs an effective double-chamber photoelectrocatalysis system for degrading terramycin, realizes synchronous degradation of terramycin on a cathode and an anode, prepares the titanium dioxide nanotube array photoelectrode with good electrode stability, high photoelectric conversion efficiency, high photocatalytic activity, green and pollution-free performance and visible light photocatalytic activity, and realizes efficient degradation of terramycin by applying the photoelectrode to the double-chamber photoelectrocatalysis system
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The method for degrading terramycin by double-chamber photoelectrocatalysis is characterized by comprising the following specific steps:
s1: construction of double-chamber photoelectrocatalysis System
Connecting two quartz reactors with communicating pipes at the bottoms, adding a cation exchange membrane in the middle, respectively using self-made titanium dioxide nanotube array photoelectrodes doped with graphite phase carbon nitride as an anode and a cathode of a photoelectrocatalysis system, switching on the anode and the cathode, and irradiating the anode by using a xenon lamp;
s2, degrading terramycin by using photoelectric catalytic system
Adding a terramycin solution with a certain concentration into a reactor of the double-chamber photoelectrocatalysis system, turning on a xenon lamp, adjusting an external bias voltage, and degrading terramycin;
the graphite phase carbon nitride doped titanium dioxide nanotube array photoelectrode is prepared by adopting a one-step method, and the specific method is as follows: in a graphite-phase carbon nitride, anhydrous sodium sulfate and sodium fluoride mixed system solution, a pretreated titanium sheet is used as an anode, a platinum sheet is used as a cathode, and after anodic oxidation under a certain voltage condition, the oxidized titanium sheet anode is placed in a muffle furnace for high-temperature annealing, so that a self-made graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode is obtained;
in the step S1, the power supply for connecting the anode and the cathode is a direct current stabilized voltage power supply, the distance between the xenon lamp and the anode reactor is 1-3cm, and the power of the xenon lamp is 100-150W.
2. The method of claim 1, wherein the concentration of oxytetracycline in the reactor in step S2 is 10-50mg/L, the xenon lamp is turned on simultaneously with an applied bias in the range of 0.5-1.5V, and the reaction temperature is 15-30 ℃.
3. The method according to claim 1, wherein the titanium content in the titanium sheet is more than 99.9%, and the pretreatment method of the titanium sheet is as follows: washing off the surface oxide layer by using hydrofluoric acid, washing by using clear water, polishing by using sand paper, and cleaning the polished titanium sheet by using a cleaning agent.
4. The method of claim 3, wherein the cleaning agent is one or more of ethanol, acetone, and deionized water.
5. The method of claim 1, wherein the graphite phase carbon nitride is prepared by the following method: calcining melamine at 400-550 ℃, naturally cooling to room temperature after calcining, and grinding and crushing to obtain graphite-phase carbon nitride.
6. The method of claim 1, wherein the precursor of graphite-phase carbon nitride in step S2 comprises one or both of melamine and urea.
7. The method of claim 1, wherein the titanium sheet has an anodic oxidation voltage of 15 to 30V, a muffle annealing temperature of 450 to 600 ℃, and an annealing time of 1 to 6h.
8. The method of claim 1, wherein the mixed system solution is prepared from graphite phase carbon nitride with a concentration of 0.2-1g/L, anhydrous sodium sulfate with a concentration of 0.5-1mol/L and a sodium fluoride solution with a concentration of 0.2-0.6 wt%.
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