CN113083273B - 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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- CN113083273B CN113083273B CN202110396086.4A CN202110396086A CN113083273B CN 113083273 B CN113083273 B CN 113083273B CN 202110396086 A CN202110396086 A CN 202110396086A CN 113083273 B CN113083273 B CN 113083273B
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
The invention discloses a method for modifying titanium dioxide by plasma induced carbon doping 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 tubular furnace cavity, and introducing inert gas to remove air; and S3, adjusting the vacuum degree and the temperature in the cavity of the tubular furnace to ensure that the vacuum degree is 10-100 Pa and the temperature is 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 titanium dioxide after plasma induced carbon doping modification. 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 the defects of low quantum efficiency and low utilization rate of visible light because the forbidden band width of titanium dioxide is 3.2 ev. 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 expanded 2 Response range in the visible region. Wherein, the metal/nonmetal doping has better modification effect, wherein, the carbon element is doped into the titanium dioxide to generate a surface state close to a valence band,free hydroxyl can be formed under the excitation of visible light, and higher photocatalytic activity is shown. 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 complex conditions and high cost, and is inconvenient for industrialized popularization and application.
It is seen that improvements and enhancements in 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 process for plasma-induced carbon doping of modified titanium dioxide, wherein the process comprises the steps of:
step 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: adjusting the vacuum degree and the temperature in the cavity of the tubular furnace to make the vacuum degree between 10 and 100Pa and the temperature between 20 and 200 ℃, continuously introducing inert gas, starting a plasma excitation source, carrying out plasma induction treatment for 5 to 40min under the power of 100 to 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 the 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 doping modified titanium dioxide by plasma-induced carbon, in the steps S2 and S3, the inert gas is one of argon and nitrogen.
In the method for doping modified titanium dioxide by plasma-induced carbon, in the step S3, the flow rate of the inert gas is 40-60 mL/min.
In the method for modifying titanium dioxide by plasma-induced carbon doping, in the step S3, the temperature is 60-80 ℃.
In the method for modifying titanium dioxide by plasma-induced carbon doping, 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 tubular 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 beneficial effects 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 present invention provides a plasma-induced carbon-doped modified titanium dioxide and a photocatalyst, and in order to make the objects, technical schemes and effects of the present invention clearer and clearer, the present invention will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not 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: 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 solid particles obtained by separation 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 organic matter adsorption, the higher the temperature is, the larger the adsorption amount of the organic matter is, and the high temperature can promote the molecular rearrangement of the organic matter, so as to improve the uniformity, but the too high temperature is likely to cause the organic matter to volatilize seriously, 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 aeration speed of the inert gas is 20-100 mL/min, the aeration time is 10-20 min, and the inert gas atmosphere in the cavity of the tubular furnace is ensured through evacuation and aeration.
S3, plasma-induced carbon-doped modified titanium dioxide: after exhausting the air in the tubular furnace cavity, 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 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 cavity of the tube furnace is 60 to 80 ℃. The temperature of the cavity of the tubular furnace is a key factor influencing the doping amount, and is too low to release carbon atoms from organic matters coated on the surface, so that the carbon cannot enter oxygen vacancies, the proportion of carbon doping is too low, the band gap change of a forbidden band is small, and the obtained titanium dioxide still maintains ultraviolet response. While too high a temperature will result in excessive carbon doping and, conversely, reduced oxygen vacancies, affecting 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 more oxygen vacancies exist, so that the light response range is expanded, and meanwhile, better photocatalytic activity and efficiency are maintained.
Preferably, in the method of plasma-induced carbon doping modified titanium dioxide, in step S1, the particle size of the nano titanium dioxide is 2 to 10nm. 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 degree of vacuum is 20 to 50Pa. 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 TiO 2 Generation of Ti in crystal lattice 3+ 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 TiO 2 The forbidden band of the titanium dioxide is narrowed, the forbidden band gap of the titanium dioxide 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 defect sites can enable the surface of titanium dioxide to form a layer of active surface, 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 dark light conditions; 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 stronger photocatalytic activity and stronger adsorption action, can respond to ultraviolet light and visible light with the wavelength of 450-800 nm, so that the photocatalyst 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 stronger adsorption action, so that the 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 tubular furnace to keep the vacuum degree in the cavity of the tubular furnace within the range of 90-100 Pa, continuously filling inert gas, regulating the flow of nitrogen to be 40mL/min, heating the cavity of the tubular furnace to 200 ℃ at the heating rate of 10 ℃/min, starting a plasma excitation source, carrying out plasma induction treatment for 5min under 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 serving as protective gas into the furnace 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 serving as protective gas into the furnace 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 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 20-30 Pa, continuously filling inert gas, adjusting the flow of nitrogen to be 55mL/min, heating the cavity of the tubular 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) crystal plane; 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 determined to be anatase-phase TiO2 in sample 2 by comparing it with a standard card (PDF-21-1272), and the peak appearing at 2 θ =25.3 ℃ was anatase TiO 2 The 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 species 2 Eg, B1g, A1g and Eg patterns of the phases.
In FIG. 4, the infrared spectrum measurement range is 4000-400 cm -1 ，3200～3500cm -1 Peaks in the range of TiO 2 Stretching vibration of O-H bond caused by water adsorption on the surface; 2700-3000 cm -1 Is benzeneC-H in methanol 2 Telescopic vibration of the key; 1500-1800 cm -1 The peak in the range is the oscillation peak of O-H. 1200-1500 cm -1 Peaks in the range are from stretching vibrations of the C-OH bond in benzyl alcohol; 1000cm -1 The following peak is the stretching vibration of the Ti-O-Ti bond. The difference between the two is that the carbon is doped with 1000-1300 cm of modified titanium dioxide -1 The range of the stretching vibration corresponding to Ti-O bond and C-O bond is 500-1000 cm -1 The 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 TiO 2 In crystal lattice Ti 4+ The relevant Ti 2P3/2 and Ti 2P1/2 orbitals correspond to that the binding energy of the Ti 2P3/2 and the Ti 2P1/2 is slightly changed compared with the unmodified nano titanium dioxide. The above results show that: ti is caused due to lattice distortion and C atom has electronegativity lower than that of O atom 3+ The appearance in the carbon-doped modified titanium dioxide sample. Meanwhile, as can be seen from FIG. 5C, for the carbon-doped modified titanium dioxide, there are three peaks at 284.8, 286.3 and 289.1eV, which are respectively assigned to 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 TiO 2 In interstitial sites of the crystal lattice, the introduction of C atoms as dopants is thereby achieved. As can be seen in FIG. 5d, the O1s peak of the carbon-doped modified titania can be fitted to three peaks after deconvolution, with the peak occurring at 530.1eV being derived from the TiO peak 2 The peak at 532.3eV of Ti-O-Ti in the lattice is due to the Ti-O-C bond, and the last peak 531.2eV is due to the O-H bond. The O-H peak shifts to lower energy than unmodified nano-titania, probably due to adsorption on TiO 2 Adsorption of surfacesWater 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.
From fig. 7, it can be seen that 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 band gap of the modified titania is reduced by a lot, and it is because the band gap of the forbidden band is small, so that the carbon-doped modified titania has the characteristic of visible light response.
(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 -5 Adding 50mg of carbon-doped modified titanium dioxide and unmodified nano titanium dioxide prepared in the examples 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 irradiating for 100min, measuring the concentration of rhodamine B once every 20min during the illumination period, and using the mixed solution with visible light of 450nm
The degradation performance is shown, wherein C represents the concentration of rhodamine B detected at corresponding time, C0 is the initial concentration of rhodamine B, and the detection result is shown in Table 1. In addition, the concentration of rhodamine B is measured by using an ultraviolet spectrophotometerAnd (5) detecting the line.
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
It can be seen that the concentration of rhodamine B in the samples described in examples 1 to 5 suddenly decreased, while the concentration of rhodamine B in comparative examples 1 and 2 did not change much, and therefore, the carbon-doped modified titania described in examples 1 to 5 was able to remove a portion of rhodamine B by adsorption, and therefore, the carbon-doped modified titania still had the effect of removing organic contaminants even under dark light conditions. After 40min of illumination, the photocatalyst described in the examples 1-5 can remove nearly 90% of rhodamine B, after 60min of illumination, the photocatalyst can completely remove rhodamine B, and has higher photocatalytic degradation efficiency, while the photocatalyst described 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 used for sewagePurification, coating 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 (6)
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, wherein the particle size of the nano titanium dioxide is 2-10 nm, the organic solvent comprises one of ethanol, glycerol, toluene and benzyl alcohol, 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: adjusting the vacuum degree and the temperature in the cavity of the tubular furnace to make the vacuum degree of the cavity of the tubular furnace be 10-100 Pa and the temperature be 20-200 ℃, simultaneously continuously introducing argon or nitrogen, wherein the flow rate of the argon or the nitrogen is 40-60 mL/min, 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 the temperature in step S3 is 60-80 ℃.
3. The method for inducing carbon doping of modified titanium dioxide according to claim 1, wherein the degree of vacuum in step S3 is 20 to 50Pa.
4. The method for inducing carbon doping modification titanium dioxide by using plasma according to claim 1, wherein 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 the plasma excitation source is 300W.
5. A photocatalyst, characterized in that the photocatalyst is titanium dioxide, which is prepared by the method of any one of claims 1 to 4.
6. The photocatalyst as claimed in claim 5, wherein the visible light wavelength response range of the photocatalyst is 450 to 800nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010021454A2 (en) * | 2008-08-18 | 2010-02-25 | Inha-Industry Partnership Institute | Method of preparing carbon-doped titanium dioxide nanoparticles by decompositing carbon dioxide using thermal plasma |
| ITMI20091764A1 (en) * | 2009-10-14 | 2011-04-15 | Italcementi Spa | PROCEDURE FOR THE PREPARATION OF DOPED TITANIUM DIOXIDE WITH CARBON |
| WO2015022267A1 (en) * | 2013-08-14 | 2015-02-19 | Solvay Sa | Process for the manufacture of propanediol |
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