CN109569684B - Plasma modified metal oxide and g-carbon nitride co-modified titanium dioxide nanorod composite photocatalyst as well as preparation method and application thereof - Google Patents
Plasma modified metal oxide and g-carbon nitride co-modified titanium dioxide nanorod composite photocatalyst as well as preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 33
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- 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
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a metal oxide and g-carbon nitride co-modified titanium dioxide nanorod composite photocatalyst as well as preparation and application thereof, (1) the metal oxide and g-C are respectively treated by adopting a dielectric barrier discharge plasma method3N4Modifying; or para-metal oxide-g-C3N4Modifying the compound; (2) for modified metal oxide and modified g-C3N4Carrying out distributed electrodeposition or modifying metal oxide-g-C3N4One-step electrodeposition of the compound; (3) and (4) after the electrodeposition is finished, airing and calcining in a nitrogen atmosphere to obtain the catalyst. The preparation method is simple and easy to prepare, and the prepared catalyst has stable and efficient actual application effect and can synergistically degrade mixed pollutants of phenol and heavy metal hexavalent chromium.
Description
Technical Field
The invention relates to a method for synthesizing metal oxide and g-C by using dielectric barrier discharge plasma auxiliary method3N4A preparation method of a co-modified titanium dioxide nanorod composite photoelectric catalyst belongs to the technical field of photoelectric catalytic materials.
Background
In recent years, photocatalytic technology has been considered as the most potential means for solving energy problems and environmental pollution. Nano TiO 22The photocatalyst is the most attention-paid type in the family of photocatalytic materials, has the advantages of high efficiency, stable chemical properties, no toxicity, no harm, low price and the like, and has been the most attention-paid photocatalyst since the discovery in 1972.
For example, the Chinese invention with the publication number of CN105597723A discloses a supported TiO2Method for preparing photocatalyst using TiO2Inorganic active carbon is attached to the sol and is calcined by a muffle furnace to prepare and produce inorganic active carbon supported TiO2A photocatalyst. The Chinese invention with the publication number of CN1105032479A discloses a TiO2The invention discloses a preparation method of a photocatalyst, which relates to the technical field of chemical industry and adopts an acid catalysis sol-gel method to prepare natural zeolite supported TiO by taking natural zeolite as a carrier and tetrabutyl titanate as a precursor2A photocatalyst.
But nano TiO2The photocatalytic efficiency and the utilization of visible light are still insufficient, and TiO2The forbidden band width of the film is 3.2eV, and the film can only absorb and utilize the ultraviolet light accounting for less than 5 percent of the total amount in the sunlight and can not fully utilize the visible light part in the solar energy, in order to solve the problem of TiO2Due to the defects, researchers modify the defects by adopting various means such as semiconductor compounding, ion doping, precious metal deposition and the like.
g-C3N4Because of its high thermal stability, chemical stability and electronic properties, it is a new favorite of research in the field of photocatalysis. The chemical vapor deposition and electrodeposition of TiO by researchers2And g-C3N4Are combined together to obtainHigh-efficiency photoelectrocatalysis property is obtained, but the existing catalysts have the problems of complex preparation method, harsh reaction conditions or further improvement of catalyst performance.
Disclosure of Invention
The invention provides a titanium dioxide nanorod composite photocatalyst co-modified by metal oxide and g-carbon nitride, and a preparation method and application thereof.
A metal oxide and g-C3N4The preparation method of the co-modified titanium dioxide nanorod composite photocatalyst is characterized by comprising the following steps:
(1) respectively processing metal oxide and g-C by dielectric barrier discharge plasma method3N4Modifying; or treating the metal oxide-g-C by adopting a dielectric barrier discharge plasma method3N4Modifying the compound;
(2) firstly, taking a solution containing modified metal oxide as an electrodeposition solution, FTO conductive glass loaded with titanium dioxide nanorods as a working electrode, a titanium sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode to carry out electrodeposition to obtain an intermediate electrode, and then taking a solution containing g-C3N4The solution is electrodeposition solution, the obtained intermediate electrode is a working electrode, the titanium sheet is a counter electrode, and the Ag/AgCl electrode is a reference electrode for electrodeposition;
or by containing modified metal oxide-g-C3N4The solution of the compound is an electrodeposition solution, FTO conductive glass loaded with titanium dioxide nano rods is a working electrode, a titanium sheet is a counter electrode, and an Ag/AgCl electrode is a reference electrode for electrodeposition;
(3) and (4) after the electrodeposition is finished, airing and calcining in a nitrogen atmosphere to obtain the catalyst.
Dielectric barrier discharge, as a representative cold plasma generator, "gas discharge" refers to the generation of a strong non-equilibrium plasma at atmospheric pressure and moderate gas temperatures, creating a dielectric barrier between two separate electrodes. Dielectric barrier discharge suitable forThe method can be used in various fields such as pollutant removal, nano material synthesis and analysis application, and can be attributed to unique advantages of the method, including mild discharge, small volume, simple structure and low power consumption. During discharge, a higher energy density is provided compared to conventional techniques. To date, most research has been limited to the in situ reduction of noble metal ions on various substrate materials to use H2As a working gas, to generate a complex in the dielectric barrier discharge plasma. In the prior art, it is still rare and limited to use electrical discharges in air to make metal oxide composites.
The graphite carbon nitride modified by dielectric barrier discharge plasma can greatly improve g-C3N4And the g-C is improved by doping modification of O and N3N4The photoelectric properties of (a); dielectric barrier discharge plasma modified Ag2The O nanomaterial exhibits crystallinity with a slight shift in diffraction angle, and this material can exhibit excellent redox performance even at high temperatures. g-C3N4And Ag2The combination of O has good matching property, p-n heterojunction can be easily manufactured,
this will result in a more efficient interfacial transfer of photo-generated electrons and holes compared to conventional composites. In addition, Ag2O nanoparticles dispersed in g-C3N4This can greatly reduce the use of Ag to improve photocatalytic activity.
Dielectric barrier discharge plasma modified g-C3N4-Mn3O4The composite has a significant effect, the size of the resulting catalyst becomes smaller, its specific surface area is larger, exposing more active sites. Mn3O4The particles are in g-C3N4Has better dispersibility and promotes the degradation of pollutants. The dielectric barrier discharge plasma-assisted synthesis is solvent-free and can be rapidly carried out at room temperature without additional oxidizing/reducing agents.
The g to C3N4Commercially available or prepared by the following method:
a certain amount of melamine is weighed and placed in a crucible, inHeat treatment in a muffle furnace followed by grinding for 1 hour to yield the product g-C3N4. Wherein the heat treatment conditions are as follows: heating to 520 ℃ in a muffle furnace at the heating rate of 5 ℃/min, and keeping the temperature for 4 h.
The FTO conductive glass loaded with the titanium dioxide nanorods as the working electrode is commercially available and can also be prepared by the following method:
(1) ultrasonically cleaning FTO conductive glass for 15min by using acetone, absolute ethyl alcohol and deionized water in sequence, and then drying;
(2) preparing a hydrochloric acid solution, placing the hydrochloric acid solution in a 50mL beaker, covering with a preservative film, sealing and stirring for 10min, adding tetrabutyl titanate and stirring for 5 min;
(3) and (3) obliquely placing the cleaned FTO conductive glass in the autoclave body, enabling the conductive surface of the glass to face upwards, adding the prepared solution, screwing the autoclave, placing the autoclave in an oven, and heating at 170 ℃ for 4 hours to obtain the titanium dioxide nanorod.
Preferably, the metal oxide is Ag2O or Mn2+An oxide.
Ag2O is commercially available or can be prepared by the following method:
NaOH was taken in distilled water and stirred for 30 minutes. 0.1M AgNO was added dropwise with stirring3Continuously stirring the mixture for 30 minutes under dark conditions, centrifuging to collect the product and washing with distilled water several times, and finally drying the solid product at 60 ℃ overnight to obtain Ag2O。
Mn2+The oxides are commercially available and can also be prepared by the following method:
mixing MnCl2·4H2O was added to deionized water. Ultrasonic treatment for 30 minutes, and then keeping the temperature in a vacuum oven at 80 ℃ for 2 hours to obtain Mn2+An oxide.
Preferably, the conditions for modifying the dielectric barrier discharge plasma method in step (1) are as follows: the voltage is 30-45V, and the time is 10-40 min. The modification time is more preferably 10 to 30min, and most preferably 20 min.
In the present invention, plasma treatment is used to alter g-C3N4Surface property, can improve g-C3N4Specific surface area of (2) to promote powder uniformityDispersing, improving the photocatalytic performance of the material and obviously enhancing the performance of photocatalytic degradation of pollutants. g-C treated by dielectric barrier discharge plasma reactor3N4The powder greatly improves the photoelectric property of the titanium dioxide nano-rod, and g-C is easy to damage by plasma modification for a long time3N4The active sites on the surface and the surface appearance of the material influence the catalytic performance of the catalyst, and the modification in too low time cannot achieve the doping of dispersed catalyst and O, N active substances and the purpose of catalyst modification, so that the optimal catalyst modification is facilitated by controlling the modification time of the catalyst under the optimal conditions.
Preferably, the solution containing the modified metal oxide in the step (2) is an ethylene glycol solution of the metal oxide, and the concentration of the metal oxide in the ethylene glycol solution is 0.2-0.8 mg/mL; containing g-C3N4In the solution of (1) g-C3N4The ethanol solution of (1), the ethanol solution containing g-C3N4The concentration of (A) is 0.8-1.2 mg/mL; containing modified metal oxide-g-C3N4The solution of the compound is glycol solution of the compound, and the glycol solution contains metal oxide-g-C3N4The concentration of the compound is 2-3 mg/mL.
Further preferably, the solution containing the modified metal oxide in the step (2) is an ethylene glycol solution of the metal oxide, and the concentration of the metal oxide in the ethylene glycol solution is 0.4-0.6 mg/mL; containing g-C3N4In the solution of (1) g-C3N4The ethanol solution of (1), the ethanol solution containing g-C3N4The concentration of (A) is 0.9-1.1 mg/mL; containing modified metal oxide-g-C3N4The solution of the compound is glycol solution of the compound, and the glycol solution contains metal oxide-g-C3N4The concentration of the compound is 2.4-2.6 mg/mL.
Most preferably, the solution containing the modified metal oxide in the step (2) is an ethylene glycol solution of the metal oxide, and the concentration of the metal oxide in the ethylene glycol solution is 0.5 mg/mL; containing g-C3N4In the solution of (1) g-C3N4The ethanol solution of (a) is added,g-C in the ethanol solution3N4The concentration of (A) is 1 mg/mL; containing modified metal oxide-g-C3N4The solution of the compound is glycol solution of the compound, and the glycol solution contains metal oxide-g-C3N4The concentration of the complex was 2.5 mg/mL. The ethanol is 50% ethanol.
Under the above-mentioned preferred conditions: oxygen-containing species, including O, generated by collisions and energy transfer between oxygen molecules and energetic electrons in the plasma2 -，O3Etc., highly active, having a higher oxidizing power for molecular oxygen, will react with absorbed Ag+/Mn2+Reaction to form at g-C3N4Ag modified on surface2O/Mn3O4. The composite material can be obtained only in a few minutes with the help of dielectric barrier discharge plasma. The dielectric barrier discharge plasma-assisted synthesis is solvent-free and can be rapidly carried out at room temperature without additional oxidizing/reducing agents.
Preferably, the metal oxide-g-C3N4The compound is prepared by the following method:
g to C3N4Adding the powder and the metal oxide precursor into deionized water, carrying out ultrasonic treatment until the adsorption is balanced, and then drying in a vacuum oven to obtain the catalyst. And then placed in a plasma discharge reactor for discharge treatment. The product is washed clean with deionized water to remove unreacted oxides and finally dried in an oven.
In the step (1), Ag can be modified by single plasma2O、Mn3O4、g-C3N4Or to Ag2O/g-C3N4、Mn3O4/g-C3N4Co-modifying the mixture; the single Ag can be obtained after the modification of the step (1)2O、Mn3O4、g-C3N4Or Ag2O/g-C3N4、Mn3O4/g-C3N4And (3) mixing.
Preferably, all electrodeposition process conditions in step (2) are: and carrying out electrodeposition for 10-20 min under the condition of-0.4 to-0.8V.
The stability of the electrode material is affected by over-high voltage, the electrode is easy to be damaged or the surface of the electrode is easy to fall off, and the metal oxide and g-C cannot be effectively deposited when the voltage is too low3N4For metal oxides and g-C3N4Is the effective deposition voltage. Meanwhile, the metal oxide and g-C are easy to form when the deposition time is too long3N4Excessive deposition, uneven deposition on the surface of the electrode, easy peeling and uneven thickness, affect the service life of the electrode, and too short deposition time can not form uniform and compact metal oxide and g-C on the surface of the electrode3N4Thin films, also affect the preparation of the electrodes. Within the above preferred ranges, the electrode produced is of better quality.
More preferably: electrodepositing for 15min under the condition of-0.4 to-0.8V; most preferably: electrodepositing for 15min under-0.6V.
Preferably, the calcining condition in the step (3) is constant temperature calcining at 350-450 ℃ for 1-1.5 hours.
The invention also provides the metal oxide and g-C prepared by the preparation method3N4Co-modifying titanium dioxide nano-rod composite photocatalyst.
The invention also provides an electrochemical treatment method of the organic polluted wastewater, which comprises the following steps:
with said metal oxide and g-C3N4The co-modified titanium dioxide nanorod composite photocatalyst is used as an anode, the titanium sheet is used as a cathode, a bias voltage of 2-4V is applied, and organic polluted wastewater is electrolyzed for 1.5-2.5 hours.
Preferably, the electrolyte solution is 0.1M Na2SO4The contaminants selected were phenol and chromium (VI).
Compared with the prior art, the invention synthesizes the metal oxide and g-C by using a dielectric barrier discharge plasma auxiliary method3N4The method for co-modifying the titanium dioxide nanorod composite photocatalyst brings the following technical effects:
(1) the raw materials used in the invention are cheap, the preparation method is simple, the cost is low, the efficiency is high, no pollutant is generated in the preparation process, and the method is favorable for further realizing large-scale production;
(2) the nano composite material prepared by the method has more reactive active sites, and because the photocatalytic reaction mainly occurs on the surface of the photocatalyst, the relatively larger specific surface area has more reactive active sites which have obvious promotion effect on the catalytic performance of the photocatalyst, thereby improving the degradation rate of pollutants.
Drawings
FIG. 1 shows the synthesis of g-C by dielectric barrier discharge plasma assisted method, prepared in example 13N4A photocurrent diagram of the titanium dioxide nanorod composite photocatalytic electrode;
FIG. 2 shows the synthesis of g-C by dielectric barrier discharge plasma assisted method, prepared in example 13N4Scanning electron microscope images of the titanium dioxide nanorod composite photocatalytic electrode;
FIG. 3 shows the synthesis of g-C by dielectric barrier discharge plasma-assisted method in example 23N4Degrading phenol and hexavalent chromium in a plasma reactor by using the titanium dioxide nanorod composite photocatalytic electrode;
FIG. 4 shows the synthesis of g-C by dielectric barrier discharge plasma-assisted method in example 33N4Degrading phenol and hexavalent chromium with a titanium dioxide nanorod composite photocatalytic electrode, wherein a deuterium lamp is used as a light source;
FIG. 5 shows the synthesis of Ag by dielectric barrier discharge plasma-assisted method in example 42O and g-C3N4A photocurrent graph of the co-modified titanium dioxide nanorod composite photocatalytic electrode;
FIG. 6 shows the synthesis of Ag by dielectric barrier discharge plasma-assisted method in example 42O and g-C3N4And degrading phenol and hexavalent chromium by using the co-modified titanium dioxide nanorod composite photocatalytic electrode as a degradation efficiency graph with a deuterium lamp as a light source.
FIG. 7 shows the synthesis of Mn by dielectric barrier discharge plasma assisted method as prepared in example 63O4And g-C3N4And (3) a photoelectricity diagram of the co-modified titanium dioxide nanorod composite photocatalytic electrode.
Detailed Description
Example 1
(1) For g-C by dielectric barrier discharge plasma method3N4Modifying the powder
Taking a proper amount of g-C3N4And (3) placing the powder in a dielectric barrier discharge plasma reactor, using air as a working gas, and starting a plasma reaction at a voltage of 30V, wherein the reaction time is 0-40 min, more preferably 10-30 min, and most preferably 20 min.
(2)g-C3N4Preparation of modified titanium dioxide nanorod electrode
Adding 0.1g of g-C modified by a dielectric barrier discharge plasma reactor into 100mL of 50% ethanol solution3N4And (3) continuously stirring the powder, performing ultrasonic treatment for 12 hours, centrifuging the powder, and taking supernatant as an electro-deposition solution. Performing electrodeposition by using an electrochemical workstation and a three-electrode system, taking a titanium dioxide nanorod prepared by a hydrothermal method as a working electrode, a titanium sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode, and performing electrodeposition for 15 minutes under the condition that the electrodeposition voltage is-0.6V. Air-drying at room temperature, calcining at 400 deg.C for 1 hr in nitrogen atmosphere to obtain g-C3N4Modifying the titanium dioxide nanorod electrode.
LSV characterization of the electrode was performed using CHI660E electrochemical workstation, and g-C after dielectric barrier discharge plasma reactor treatment can be seen from LSV photo-amperometry (as shown in FIG. 1)3N4The powder greatly improves the photoelectric property of the titanium dioxide nano-rod and is in g-C3N4After the powder is modified for 20min, the photocurrent density is improved by nearly three times.
The surface topography of the composite electrode prepared in example 1 was characterized using a field emission scanning electron microscope (see FIG. 2), in which g-C can be seen3N4Successfully and uniformly distributed on the titanium dioxide nano-rods.
Example 2
Use implementationThe composite electrode prepared in example (1) was treated with 80. mu. mol/L (100mL) of a hexavalent chromium solution, 10mg/L (100mL) of a phenol solution, and 0.1M Na2SO4The degradation is carried out in a dielectric barrier discharge plasma reactor as an electrolyte solution, the voltage is 30V, a sample is taken for 10min, and the reaction is carried out for one hour. The experimental results are shown in fig. 3, and it can be seen that hexavalent chromium is completely removed after 10 min.
Example 3
Using the composite electrode prepared in example (1), 80. mu. mol/L (100mL) of a hexavalent chromium solution, 10mg/L (100mL) of a phenol solution, treated with 0.1M Na2SO4Is electrolyte solution, with an external bias of 3V, and is adsorbed in dark for 30min before the light power is turned on, so as to reach adsorption and desorption balance.
And sampling once in half an hour, and reacting for two hours. The results of the experiment are shown in fig. 4, and it can be seen that the hexavalent chromium removal rate is about 70% after 2 hours.
Example 4
(1)Ag2O-5/TiO2Preparation of-NRs
0.05g of Ag modified by plasma for 5min is taken2Dissolving O powder in 100mL of glycol, and performing ultrasonic dispersion for 30 min. The solution is used as an electrodeposition solution, a titanium dioxide nanorod prepared by a hydrothermal method is used as a working electrode, a titanium sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and electrodeposition is carried out for 30min under the condition that the electrodeposition voltage is-0.6V. Washing with deionized water after the deposition process is finished, and drying to obtain Ag2O/TiO2-NRs；
(2)Ag2O-5/g-C3N4-5/TiO2Preparation of-NRs
Electrodeposition was carried out using an electrochemical workstation using a three-electrode system, using the solution obtained in example 1 as the electrodeposition solution and Ag2O-5/TiO2And (4) carrying out electrodeposition for 15 minutes under the condition that the electrodeposition voltage is-0.6V by taking the-NRs as a working electrode, the titanium sheet as a counter electrode and the Ag/AgCl electrode as a reference electrode. Air-drying at room temperature, calcining at 400 deg.C for 1 hr in nitrogen atmosphere to obtain Ag2O-5/g-C3N4-5/TiO2-NRs。
Electrode feeding using CHI660E electrochemical workstationLine LSV characterization, from LSV light current chart (as shown in FIG. 5), it can be seen that Ag treated by the dielectric barrier discharge plasma reactor for 5min2O-5/g-C3N4-5 powder comparison unmodified g-C3N4The powder greatly improves the photoelectric property of the titanium dioxide nano-rod.
Example 5
Using the composite electrode prepared in example (4), 160. mu. mol/L (100mL) of a hexavalent chromium solution, 10mg/L (100mL) of a phenol solution, treated with 0.1M Na2SO4Is electrolyte solution, with an external bias of 3V, and is adsorbed in dark for 30min before the light power is turned on, so as to reach adsorption and desorption balance. And sampling once in half an hour, and reacting for two hours. The results of the experiment are shown in FIG. 6, after 2h, the phenol removal was about 70%.
Example 6
Mn3O4/g-C3N4Preparing a composite material: 2mL of deionized water was taken and added with 0.2g, 0.4g, 0.6g, 1.0g, 1.5g of g-C3N4And (3) powder. Then adding Mn2+Adding into the solution of original g-C3N4Powder in 2mL deionized water. After sonication, the mixture was kept in a vacuum oven at 80 ℃ for 2 hours. It was then placed in a plasma discharge reactor at 45V for 10 min. Product (expressed as Mn)3O4/g-C3N4X, X represents g-C3N4Added amount) was washed with deionized water to remove unreacted Mn2+And finally drying in an oven at 80 ℃.
Respectively taking 2.5mg/mL of Mn3O4/g-C3N4And (4) carrying out ultrasonic dispersion for 30min by using an-X ethylene glycol solution. The prepared grown TiO2And soaking the FTO electrode of the nanorod in the ultrasonic solution for 30min, wherein the conductive surface faces upwards. Finally in N2Raising the temperature to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere lower tube furnace, and keeping the temperature for 1 hour.
FIG. 7 shows different Mn after DBD plasma reactor treatment3O4/g-C3N4LSV photo-amperometric diagram of photoelectric properties of the titanium dioxide nanorods according to the dosage of the X powder. It can be seen that the initial g-C3N4The addition of (B) has obvious influence on the photoelectric property of the prepared electrode, and Mn3O4/g-C3N4Photocurrent density of-0.4 was Mn3O4/g-C3N4Approximately five times 1.5.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (4)
1. A metal oxide and g-C3N4The preparation method of the co-modified titanium dioxide nanorod composite photocatalyst is characterized by comprising the following steps:
(1) respectively processing metal oxide and g-C by dielectric barrier discharge plasma method3N4Modifying; the metal oxide is Ag2O; the conditions of the dielectric barrier discharge plasma method modification are as follows: the voltage is 30-45V, and the time is 10-40 min;
(2) firstly, taking a solution containing modified metal oxide as an electrodeposition solution, FTO conductive glass loaded with titanium dioxide nanorods as a working electrode, a titanium sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode to carry out electrodeposition to obtain an intermediate electrode, and then taking a solution containing modified g-C3N4The solution is electrodeposition solution, the obtained intermediate electrode is a working electrode, the titanium sheet is a counter electrode, and the Ag/AgCl electrode is a reference electrode for electrodeposition; the solution containing the modified metal oxide is an ethylene glycol solution of the metal oxide, and the concentration of the metal oxide in the ethylene glycol solution is 0.2-0.8 mg/mL; containing modified g-C3N4The solution of (a) is g-C after modification3N4The ethanol solution of (1), the ethanol solution containing g-C3N4The concentration of (A) is 0.8-1.2 mg/mL; all electrodeposition process conditions were: electrodepositing for 15min under the condition of-0.6V;
(3) after the electrodeposition is finished, drying in the air and calcining in a nitrogen atmosphere to obtain the catalyst; the calcination conditions were: calcining at 350-450 ℃ for 1-1.5 hours.
2. A metal oxide and g-C prepared by the preparation method of claim 13N4Co-modifying titanium dioxide nano-rod composite photocatalyst.
3. An electrochemical treatment method of organic polluted wastewater is characterized by comprising the following steps:
the metal oxide compound of claim 2 and g-C3N4The co-modified titanium dioxide nanorod composite photocatalyst is used as an anode, the titanium sheet is used as a cathode, a bias voltage of 2-4V is applied, and organic polluted wastewater is electrolyzed for 1.5-2.5 hours.
4. The electrochemical treatment method according to claim 3, wherein the contaminants in the organically-polluted waste water are phenol and hexavalent chromium.
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| CN112458489B (en) * | 2020-11-23 | 2021-08-31 | 浙江工商大学 | Novel catalyst material and preparation method and application thereof |
| CN113413889A (en) * | 2021-07-06 | 2021-09-21 | 辽宁师范大学 | Preparation method of amorphous vanadium catalyst for preparing phenol by benzene hydroxylation |
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