CN113083273A - Method for modifying titanium dioxide by plasma-induced carbon doping and photocatalyst - Google Patents
Method for modifying titanium dioxide by plasma-induced carbon doping and photocatalyst Download PDFInfo
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- CN113083273A CN113083273A CN202110396086.4A CN202110396086A CN113083273A CN 113083273 A CN113083273 A CN 113083273A CN 202110396086 A CN202110396086 A CN 202110396086A CN 113083273 A CN113083273 A CN 113083273A
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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Abstract
The invention discloses a method for modifying titanium dioxide by doping carbon through plasma induction and a photocatalyst, wherein the method comprises the following steps: s1, placing nano titanium dioxide in an organic solvent, stirring for 30 min-24 h at the temperature of 25-70 ℃, performing centrifugal separation, and drying to obtain a titanium dioxide precursor; s2, placing the titanium dioxide precursor in a cavity of a tubular furnace, and introducing inert gas to remove air; and S3, adjusting the vacuum degree and the temperature in the cavity of the tubular furnace to make the vacuum degree of 10-100 Pa and the temperature of 20-200 ℃, introducing inert gas, starting a plasma excitation source, and performing plasma induction treatment for 5-40 min under the power of 100-400W to obtain the plasma-induced carbon-doped modified titanium dioxide. The titanium dioxide prepared by the method of modifying titanium dioxide by plasma-induced carbon doping can be used as a photocatalyst, has visible light response and excellent photocatalytic effect, and can be widely used as a photocatalytic material.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a method for modifying titanium dioxide by plasma-induced carbon doping and a photocatalyst.
Background
The photocatalyst is a material with a photocatalytic function, can convert solar energy into chemical energy, plays roles in degrading organic pollutants, reducing heavy metals, photolyzing water to produce hydrogen and the like, and is commonly used for sewage treatment, air purification, disinfection and sterilization and the like. Among them, titanium dioxide is one of the most common photocatalysts because of its advantages such as stable structure, low cost, and environmental friendliness. However, titanium dioxide has a forbidden band width of 3.2ev, so that it has disadvantages of low quantum efficiency and low utilization rate of visible light. In the prior art, titanium dioxide is generally modified by methods such as precious metal deposition, metal/nonmetal doping, semiconductor compounding and the like, so that the forbidden bandwidth of the titanium dioxide is reduced, the energy required by electron excitation in a valence band is reduced, and TiO is expanded2Response range in the visible region. The metal/nonmetal doping has a good modification effect, wherein the carbon element is doped into the titanium dioxide to generate a surface state close to a valence band, and free hydroxyl can be formed under the excitation of visible light to show high photocatalytic activity. The existing preparation method of carbon-doped modified titanium dioxide mainly comprises a sol-gel method or a vapor deposition method, but the method and the carbon-doped modified titanium dioxide prepared by the method have more problems, such as: (1) the prepared titanium dioxide is still wide in forbidden band width and not wide in visible light response coverage; (2) the prepared titanium dioxide powder has no adsorption effect and has no catalytic degradation effect under the dark light condition; (3) the preparation process has complicated conditions and high cost, and is not convenient for industrialized popularization and application.
It is seen that improvements and enhancements to the prior art are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for inducing carbon-doped modified titanium dioxide by using plasma and a photocatalyst, and aims to overcome the defects that when titanium dioxide is used as a photocatalyst in the prior art, the visible light response is insufficient, the titanium dioxide does not have a strong physical adsorption effect, and the process of the existing preparation method for carbon-doped modified titanium dioxide is complex.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of plasma-induced carbon doping of modified titania, wherein the method comprises the steps of:
s1, preparing a titanium dioxide precursor: placing nano titanium dioxide in an organic solvent, stirring for 30 min-24 h at the temperature of 25-70 ℃, performing centrifugal separation, and drying to obtain a titanium dioxide precursor;
s2, pretreatment: placing the titanium dioxide precursor in a tubular furnace cavity, introducing inert gas into the tubular furnace cavity, and exhausting air in the tubular furnace cavity;
s3, plasma-induced carbon doping modified titanium dioxide: and adjusting the vacuum degree and the temperature in the cavity of the tubular furnace to make the vacuum degree of the cavity 10-100 Pa and the temperature 20-200 ℃, continuously introducing inert gas, starting a plasma excitation source, carrying out plasma induction treatment for 5-40 min under the power of 100-400W, and obtaining the titanium dioxide after plasma induced carbon doping modification after the reaction is finished.
In the method for plasma-induced carbon doping of modified titanium dioxide, in step S1, the organic solvent includes one of ethanol, glycerol, toluene, and benzyl alcohol.
In the method for modifying titanium dioxide by plasma-induced carbon doping, in the step S1, the particle size of the nano titanium dioxide is 2-10 nm.
In the method for plasma-induced carbon doping of modified titanium dioxide, in the steps S2 and S3, the inert gas is one of argon and nitrogen.
In the method for doping modified titanium dioxide by using plasma-induced carbon, in the step S3, the flow rate of the inert gas is 40-60 mL/min.
In the method for doping modified titanium dioxide by plasma-induced carbon, in the step S3, the temperature is 60-80 ℃.
In the method for doping modified titanium dioxide with carbon through plasma induction, in the step S3, the vacuum degree is 20-50 Pa.
In the method for modifying titanium dioxide by plasma-induced carbon doping, in the step S3, the vacuum degree in the cavity of the tube furnace is 20-30 Pa, the temperature is 60 ℃, and the power of a plasma excitation source is 300W.
The photocatalyst is titanium dioxide, and the titanium dioxide is prepared by the method for modifying titanium dioxide by plasma-induced carbon doping.
Specifically, the visible light wavelength response range of the photocatalyst is 450-800 nm.
Has the advantages that:
the invention provides a method for modifying titanium dioxide by carbon doping induced by plasma and a photocatalyst, wherein the method comprises the steps of coating organic matters on the surface of titanium dioxide, inducing by the plasma, utilizing the interaction between high-energy particles of the plasma and the titanium dioxide to generate chemical and physical synergistic reaction, inducing the surface of the titanium dioxide to be reconstructed, introducing defect sites, and replacing partial oxygen gaps with carbon, so that the band gap of the titanium dioxide is reduced, the titanium dioxide has visible light response, the photocatalysis can be realized under the irradiation of visible light, the photocatalysis efficiency is greatly improved, and meanwhile, the titanium dioxide modified by carbon doping has excellent surface physical adsorption characteristics, and organic matters can be adsorbed under the dark light condition, thereby achieving the purification effect. The carbon-doped modified titanium dioxide prepared by the method has excellent photocatalytic effect and can be widely used as a photocatalyst.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of plasma-induced carbon doped modified titania and unmodified nano-titania;
FIG. 2 is an XRD pattern of plasma-induced carbon doping of modified titania and unmodified nano-titania;
FIG. 3 is a Raman diagram of the plasma-induced carbon doping of modified titania and unmodified nano-titania;
FIG. 4 is a FTIR plot of plasma-induced carbon doping of modified titania and nano-titania before modification;
FIG. 5 is an XPS plot of plasma-induced carbon doping of modified titania and unmodified nano-titania;
FIG. 6 is a graph of the absorption spectra of plasma-induced carbon doped modified titania and unmodified nano-titania;
FIG. 7 is Tauc-plot of plasma-induced carbon doping of modified titania and unmodified nano-titania.
Detailed Description
The invention provides a plasma-induced carbon-doped modified titanium dioxide and a photocatalyst, and in order to make the purpose, technical scheme and effect of the invention clearer and clearer, the invention is further described in detail below by referring to the attached drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for modifying titanium dioxide by doping carbon through plasma induction, which comprises the following steps:
s1, preparing a titanium dioxide precursor: and (2) placing the nano titanium dioxide powder in an organic solvent, stirring for 30 min-24 h at the temperature of 25-70 ℃, performing centrifugal separation, and drying the separated solid particles to obtain a titanium dioxide precursor. The organic solvent comprises one of ethanol, glycerol, toluene and benzyl alcohol, and can be physically adsorbed on the surface of titanium dioxide in the stirring and mixing process, and an organic matter coating is formed on the surface of the titanium dioxide after drying. The organic matter coating can introduce a carbon source on the surface of the titanium dioxide to provide the carbon source for subsequent plasma-induced carbon doping, and can prevent the nano-scale titanium dioxide particles from agglomerating, so that the nano-scale particle size of the titanium dioxide particles is kept, the specific surface area of the titanium dioxide particles is increased, and the photocatalytic effect of the titanium dioxide particles is further improved. In step S1, the temperature is high or low, which affects the stability of the organic material adsorption, the higher the temperature is, the larger the organic material adsorption amount is, and the high temperature can promote the molecular rearrangement of the organic material, thereby improving the uniformity, but the too high temperature is likely to cause the organic material to be seriously volatilized, and the solvent consumption is large. When the temperature is between 25 and 70 ℃, an organic matter coating layer with uniform and moderate thickness can be formed on the surface of the nano titanium dioxide.
S2, pretreatment: placing the titanium dioxide precursor coated with the organic matters into a tubular furnace cavity, and introducing inert gas into the tubular furnace cavity to discharge air in the tubular furnace cavity to form an inert atmosphere, wherein the inert gas is one of argon and nitrogen. When air is exhausted, the ventilation speed of the inert gas is 20-100 mL/min, the ventilation time is 10-20 min, and the inert gas atmosphere in the cavity of the tubular furnace is ensured through evacuation ventilation.
S3, plasma-induced carbon doping modified titanium dioxide: after air in the tubular furnace cavity is exhausted, continuously introducing inert gas, adjusting the flow rate of the inert gas to be 40-60 mL/min, then adjusting the vacuum degree in the tubular furnace cavity by vacuumizing to enable the vacuum degree to be 10-100 Pa, simultaneously heating the tubular furnace cavity to 20-200 ℃, wherein the heating rate is 5-10 ℃/min, starting a plasma excitation source when the vacuum degree and the temperature are stable, carrying out plasma induction treatment under the power of 100-400W for 5-40 min, and obtaining the titanium dioxide after plasma induced carbon doping modification after the treatment is finished.
Specifically, in the step S3, in the plasma induction treatment process, inert gas needs to be continuously introduced to ensure that the plasma-induced carbon-doped modified titanium dioxide is performed in an inert atmosphere, the inert atmosphere can better enable lattice oxygen to escape to form oxygen vacancies, the flow rate of the inert gas can influence the escape speed of the lattice oxygen to promote the formation of the oxygen vacancies, and the continuously introduced inert gas can ensure that the hollowness of the cavity of the tube furnace is 10 to 100Pa to meet the plasma glow starting condition. In the plasma induction process, when the flow rate of the inert gas is controlled to be 40-60 mL/min, the carbon doping effect is better.
Preferably, in the step S3, the temperature in the tubular furnace cavity is 60 to 80 ℃. The temperature of the cavity of the tubular furnace is a key factor influencing the doping amount, and the temperature is too low to release carbon atoms from organic matters coated on the surface, so that the carbon cannot enter oxygen vacancies, the carbon doping proportion is too low, the forbidden band gap is slightly changed, and the obtained titanium dioxide still keeps ultraviolet response. While too high a temperature will result in excessive carbon doping and conversely in a reduction of oxygen vacancies, affecting the photocatalytic activity. Preferably, when the temperature of the cavity of the tube furnace is between 60 and 80 ℃, carbon atoms can be doped into titanium dioxide well and have more oxygen vacancies, so that the light response range is expanded, and meanwhile, the good photocatalytic activity and efficiency are maintained.
Preferably, in the method for modifying titanium dioxide by plasma-induced carbon doping, in step S1, the particle size of the nano titanium dioxide is 2 to 10 nm. The smaller the particle size of titanium dioxide is, then specific surface area is the bigger, and its absorption and photocatalysis effect then are better, and simultaneously, this application makes nanometer titanium dioxide not appear agglomerating the phenomenon through surface cladding organic matter, can keep less particle size, has better absorption effect and photocatalysis.
Preferably, in the step S3, the vacuum degree is 20 to 50 Pa. Oxygen escape is facilitated under the negative pressure condition, carbon doping is promoted, but when the vacuum degree is too low, plasma generation is influenced. When the vacuum degree is controlled to be 20-50 Pa, the generation of plasma can be promoted, and oxygen can escape.
Compared with the prior art, the method for modifying titanium dioxide by plasma induced carbon doping has the advantages of simple steps, easy realization, no need of special conditions such as high temperature and high pressure and short treatment time. In the method for modifying titanium dioxide by plasma induced carbon doping, the surface of the titanium dioxide crystal is reconstructed by the induction of plasma high-energy particles, and the reconstruction can be carried out on TiO2Generation of Ti in crystal lattice3+And introducing oxygen vacancies to form defect sites, wherein the defect sites can improve the trapping capacity of the titanium dioxide, and part of the oxygen vacancies are replaced by carbon elements under the induction action of the plasma to ensure that the TiO2The forbidden band of the titanium dioxide is narrowed, the band gap of the forbidden band can be reduced to 2.3eV, so that the photoresponse range of the titanium dioxide is widened to the wavelength range of 450-800 nm, and the obtained titanium dioxide can play a photocatalysis role under the condition of visible light; on the other hand, the defective site enables oxidation of dioxideA layer of active surface is formed on the surface of the titanium, and the active surface has stronger physical adsorption effect and can adsorb organic matters, so that the modified titanium dioxide can remove pollutants in water through physical adsorption even under the dark light condition; moreover, the surface of the titanium dioxide modified by the method is still coated with organic matters, and the organic matters can enable the modified titanium dioxide to repel each other, so that the titanium dioxide is kept in a smaller particle size, has a larger specific surface area, and greatly improves the adsorption effect and the photocatalytic effect.
The invention also discloses a photocatalyst, wherein the photocatalyst is carbon-doped modified titanium dioxide, and the carbon-doped modified titanium dioxide is prepared by the method for inducing carbon-doped modified titanium dioxide by using the plasma. The photocatalyst has strong photocatalytic activity and strong adsorption, can respond to ultraviolet light and visible light with the wavelength of 450-800 nm, can perform photocatalytic reaction under the irradiation of the visible light or the ultraviolet light, and can adsorb organic matters under the dark light condition due to the strong adsorption, so that organic pollutants in a system can be removed through strong physical adsorption even under the condition of no illumination.
To further illustrate the modified titanium dioxide doped with carbon induced by plasma and the photocatalyst provided in the present invention, the following examples are provided.
Example 1
A method of plasma-induced carbon doping of modified titanium dioxide, the method comprising the steps of:
S2, placing a titanium dioxide precursor in a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, wherein the position of the titanium dioxide precursor is 50cm away from a plasma generator, and then introducing nitrogen into the furnace as protective gas to exhaust air in the furnace;
and 3, starting a vacuum pump, vacuumizing the cavity of the tubular furnace to keep the vacuum degree in the cavity of the tubular furnace within the range of 10-20 Pa, continuously filling inert gas, adjusting the flow of nitrogen to be 40mL/min, starting a plasma excitation source at room temperature, and performing plasma induction treatment for 40min at the power of 100W to obtain an induced modified titanium dioxide sample, wherein the sample is yellow.
Example 2
A method of plasma-induced carbon doping of modified titanium dioxide, the method comprising the steps of:
S2, placing a titanium dioxide precursor in a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, wherein the position of the titanium dioxide precursor is 50cm away from a plasma generator, and then introducing nitrogen into the furnace as protective gas to exhaust air in the furnace;
and 3, starting a vacuum pump, vacuumizing the cavity of the tube furnace to keep the vacuum degree in the cavity of the tube furnace within the range of 90-100 Pa, continuously filling inert gas, adjusting the flow of nitrogen to be 40mL/min, heating the cavity of the tube furnace to 200 ℃ at the heating rate of 10 ℃/min, starting a plasma excitation source, performing plasma induction treatment for 5min at the power of 400W, and naturally cooling to obtain an induction modified titanium dioxide product, wherein the product is yellow.
Example 3
A method of plasma-induced carbon doping of modified titanium dioxide, the method comprising the steps of:
S2, placing a titanium dioxide precursor in a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, wherein the position of the titanium dioxide precursor is 50cm away from a plasma generator, and then introducing argon gas into the furnace as protective gas to exhaust air in the furnace;
and 3, starting a vacuum pump, vacuumizing the cavity of the tube furnace to keep the vacuum degree in the cavity of the tube furnace within the range of 50-60 Pa, continuously filling inert gas, adjusting the flow of argon to be 45mL/min, heating the cavity of the tube furnace to 120 ℃ at the heating rate of 8 ℃/min, starting a plasma excitation source, and performing plasma induction treatment for 15min at the power of 200W to obtain an induced modified titanium dioxide sample, wherein the sample is yellow.
The sample was named SDCT.
Example 4
A method of plasma-induced carbon doping of modified titanium dioxide, the method comprising the steps of:
S2, placing a titanium dioxide precursor in a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, wherein the position of the titanium dioxide precursor is 50cm away from a plasma generator, and then introducing argon gas into the furnace as protective gas to exhaust air in the furnace;
and 3, starting a vacuum pump, vacuumizing the cavity of the tube furnace to keep the vacuum degree in the cavity of the tube furnace within the range of 40-50 Pa, continuously filling inert gas, adjusting the flow of argon to be 60mL/min, heating the cavity of the tube furnace to 80 ℃ at the heating rate of 5 ℃/min, starting a plasma excitation source, and performing plasma induction treatment for 20min at the power of 200W to obtain an induced modified titanium dioxide sample, wherein the sample is yellow.
Example 5
A preferred method of plasma-induced carbon doping of modified titania, the method comprising the steps of:
S2, placing a titanium dioxide precursor in a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, wherein the position of the titanium dioxide precursor is 50cm away from a plasma generator, and then introducing nitrogen into the furnace as protective gas to exhaust air in the furnace;
and 3, starting a vacuum pump, vacuumizing the cavity of the tube furnace to keep the vacuum degree in the cavity of the tube furnace within the range of 20-30 Pa, continuously filling inert gas, adjusting the flow of nitrogen to be 55mL/min, heating the cavity of the tube furnace to 60 ℃ at the heating rate of 5 ℃/min, starting a plasma excitation source, and performing plasma induction treatment for 10min at the power of 300W to obtain an induced modified titanium dioxide sample, wherein the sample is yellow.
Characterization and Performance testing
(1) Characterization of
The carbon-doped modified titanium dioxide obtained in example 1 is named as 2, the unmodified nano titanium dioxide is named as 1, characterization tests are performed on 1 and 2 through TEM, XRD, Raman, FTIR, XPS, absorption spectrum and Tauc-plot respectively, the characterization test results are shown in fig. 1-7, and the specific analysis is as follows:
as shown in fig. 1, (a) is a TEM image of a nano titania sample before the unmodified treatment; (b) the figure is a TEM of sample 1 of titanium dioxide after carbon doping modification obtained for example 1. As can be seen from FIG. 1, the samples before and after modification all have smaller crystal grain sizes, the crystal grain sizes are about 5-10 nm, and the crystal plane is (101); meanwhile, the outer layer of the carbon-doped modified titanium dioxide has a defect layer.
Referring to fig. 2, the carbon-doped modified titanium dioxide was compared with a standard card (PDF-21-1272) to determine that sample 2 was anatase phase TiO2, and the peak of 2 θ ═ 25.3 ℃ was anatase TiO22The characteristic peak of (2) corresponds to the (101) crystal plane. Meanwhile, XRD test results prove that the crystal structure of the sample is not changed by the plasma-induced carbon doping modification treatment.
As can be seen from FIG. 3, the Raman spectra of the nano-titania before the unmodified treatment and the carbon-doped modified titania show three peaks at 152, 397, 514, 640cm-1, corresponding to anatase TiO species2Eg, B1g, A1g, and Eg patterns of phases.
In FIG. 4, the infrared spectrum measurement range is 4000-400 cm-1，3200～3500cm-1Peaks in the range of TiO2Stretching vibration of O-H bond caused by water adsorption on the surface; 2700-3000 cm-1Is C-H in benzyl alcohol2Telescopic vibration of the key; 1500-1800 cm-1The peak in the range is the oscillation peak of O-H. 1200-1500 cm-1Peaks in the range are from stretching vibrations of the C-OH bond in benzyl alcohol; 1000cm-1The following peak is the stretching vibration of the Ti-O-Ti bond. The difference between the carbon-doped modified titanium dioxide and the carbon-doped modified titanium dioxide is that the carbon-doped modified titanium dioxide has a thickness of 1000-1300 cm-1Corresponding to the stretching vibration of Ti-O bond and C-O bond within the range of 500-1000 cm-1The broad band in the range is caused by the mixed vibration of Ti-O-Ti bonds and Ti-O-C bonds, which indicates that carbon-doped titanium dioxide can be successfully produced by plasma-induced treatment.
Referring to fig. 5, the surface chemical states and components of the carbon-doped modified titania and the unmodified nano titania were analyzed by XPS spectroscopy, and it can be seen from fig. 5a that Ti, O, and C elements were present on the surface of the carbon-doped modified titania. In FIG. 5b, the typical peaks of the carbon-doped modified titanium dioxide at 458.8eV and 464.6eV are shown as being in contact with TiO2In crystal lattice Ti4+The relevant Ti 2P3/2 and Ti 2P1/2 orbits correspond to that of the unmodified nano titanium dioxide, and the binding energy of the Ti 2P3/2 and the Ti 2P1/2 slightly changes. The above results show that: byIn lattice distortion and C atom has electronegativity lower than that of O atom, resulting in Ti3+The appearance in the carbon-doped modified titanium dioxide sample. Meanwhile, as can be seen from FIG. 5C, for the carbon-doped modified titania, there are three peaks at 284.8, 286.3 and 289.1eV, which are respectively assigned to the C-C, C-O and Ti-O-C groups, wherein the C-O group is moved to a lower energy because benzyl alcohol is decomposed by bombardment with plasma energetic particles; secondly, the presence of a Ti-O-C bond indicates the incorporation of a C atom into the TiO2In the interstitial positions of the crystal lattice, the introduction of C atoms as dopants is thus achieved. As can be seen in FIG. 5d, the peak of O1s for the carbon-doped modified titania after deconvolution can be fit to three peaks, with the peak occurring at 530.1eV being derived from TiO2The peak at 532.3eV is due to the Ti-O-C bond, and the last peak 531.2eV is from the O-H bond. The O-H peak shifts to lower energy than unmodified nano-titania, probably due to adsorption on TiO2The adsorbed water on the surface is removed during the plasma induction process. Based on the XPS results, it is clearly shown that carbon can be successfully doped and modified with titanium dioxide by the plasma induction treatment method.
As can be seen from FIG. 6, the absorption band edge position of the carbon-doped modified titanium dioxide is 450nm, which indicates that the carbon-doped modified titanium dioxide can respond in the visible light region.
As can be seen from fig. 7, the band gap of the carbon-doped modified titania is 2.30eV, while the band gap of the unmodified nano titania is 2.97eV, and it is obvious that the modified titania has a much reduced band gap and has the characteristic of visible light response just because the forbidden band gap is small.
(2) Photocatalytic degradation Performance test
The plasma-induced carbon-doped modified titanium dioxide prepared in the examples 1 to 5 is taken as a photocatalyst to be dispersed in a rhodamine B solution, meanwhile, unmodified nano titanium dioxide is taken as a comparative example 1, and the rhodamine B solution without any photocatalyst is taken as a comparative example 2. In the photocatalytic degradation performance test, all test conditions are the same, namely, the concentration and the volume of the adopted rhodamine B solution are the same, the quality of the added photocatalyst is the same, and the illumination condition is also the same.
The specific test process is as follows: taking 7 parts of the mixture with the concentration of 2 multiplied by 10-5Adding 50mg of carbon-doped modified titanium dioxide and unmodified nano titanium dioxide prepared in the embodiments 1-5 into 100mL of mol/L rhodamine B solution respectively, wherein one part of the solution is not added with any photocatalyst, placing the sample in a dark room for stirring for 20min, measuring the concentration of rhodamine B, irradiating the mixed solution with visible light of 450nm at the illumination power of 30W, keeping stirring, turning off a visible light source after 100min of illumination, measuring the concentration of rhodamine B once every 20min during illumination, and using the mixed solution
The degradation performance is shown, wherein C represents the concentration of rhodamine B detected corresponding to time, C0 is the initial concentration of rhodamine B, and the detection results are shown in Table 1. The concentration of rhodamine B was measured by an ultraviolet spectrophotometer.
TABLE 1 photocatalytic degradation Properties
Test result table
Meanwhile, the color change of each sample was observed, and it was found that the color of the samples of examples 1 to 5 became much lighter after 20min of dark room adsorption, and at this time, the surface of the photocatalyst became red, and at the same time, the color changed from that of the samples of Table 1 after 20min of dark room adsorption
As a result, the concentration of rhodamine B in the samples described in examples 1 to 5 suddenly dropped while the concentration of rhodamine B in comparative examples 1 and 2 did not change much, and it was found thatThe carbon-doped modified titanium dioxide of examples 1 to 5 can remove part of rhodamine B by adsorption, so that the carbon-doped modified titanium dioxide still has the effect of removing organic pollutants even under dark light conditions. After 40min of illumination, the photocatalyst described in the embodiments 1-5 can remove nearly 90% of rhodamine B, after 60min of illumination, the photocatalyst can completely remove the rhodamine B, and has higher photocatalytic degradation efficiency, while the photocatalyst in the comparative example 1 still has 72% of rhodamine B even after 100min of illumination. Obviously, this is related to the carbon-doped modified titanium dioxide described in examples 1 to 5 having visible light response and strong adsorption, and thus having strong photocatalytic degradation effect, while the nano titanium dioxide described in comparative example 1 having no visible light response, thus having limited photocatalytic degradation effect, and having no adsorption capacity, thus having almost no purification ability under dark light conditions. The titanium dioxide modified by plasma induced carbon doping has the advantages of visible light response and strong adsorption capacity as a photocatalyst, and can be widely applied to the fields of sewage purification, coatings and the like.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.
Claims (10)
1. A method of plasma-induced carbon doping of modified titanium dioxide, the method comprising the steps of:
s1, preparing a titanium dioxide precursor: placing nano titanium dioxide in an organic solvent, stirring for 30 min-24 h at the temperature of 25-70 ℃, performing centrifugal separation, and drying to obtain a titanium dioxide precursor;
s2, pretreatment: placing the titanium dioxide precursor in a tubular furnace cavity, introducing inert gas into the tubular furnace cavity, and exhausting air in the tubular furnace cavity;
s3, plasma-induced carbon doping modified titanium dioxide: and adjusting the vacuum degree and the temperature in the cavity of the tubular furnace to make the vacuum degree of the cavity 10-100 Pa and the temperature of the cavity 20-200 ℃, continuously introducing inert gas, starting a plasma excitation source, carrying out plasma induction treatment for 5-40 min under the power of 100-400W, and obtaining the titanium dioxide after plasma induced carbon doping modification after the reaction is finished.
2. The method of claim 1, wherein in step S1, the organic solvent comprises one of ethanol, glycerol, toluene and benzyl alcohol.
3. The method of claim 1, wherein in step S1, the particle size of the nano-titania is 2-10 nm.
4. The method of claim 1, wherein in the steps S2 and S3, the inert gas is one of argon and nitrogen.
5. The method of claim 1, wherein in the step S3, the flow rate of the inert gas is 40-60 mL/min.
6. The method of claim 1, wherein the temperature in step S3 is 60-80 ℃.
7. The method of claim 1, wherein in the step S3, the degree of vacuum is 20-50 Pa.
8. The method of claim 1, wherein in step S3, the degree of vacuum in the cavity of the tube furnace is 20-30 Pa, the temperature is 60 ℃, and the power of the plasma excitation source is 300W.
9. A photocatalyst, wherein the photocatalyst is titanium dioxide, and the titanium dioxide is produced by the method according to any one of claims 1 to 8.
10. The photocatalyst as set forth in claim 9, wherein the photocatalyst has a visible light wavelength response range of 450 to 800 nm.
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