CN111013560A - Oxygen-deficient titanium dioxide catalyst, preparation method and application thereof - Google Patents
Oxygen-deficient titanium dioxide catalyst, preparation method and application thereof Download PDFInfo
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- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 125
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000001301 oxygen Substances 0.000 title claims abstract description 72
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 72
- 230000002950 deficient Effects 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 230000007547 defect Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 23
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
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- B01J35/39—
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention belongs to the field of synthesis of titanium dioxide photocatalytic materials, and particularly relates to an oxygen-deficient titanium dioxide catalyst and a preparation method and application thereof. A method for preparing an oxygen deficient titanium dioxide catalyst comprising the steps of: a. uniformly dispersing titanium dioxide in a plasma reactor, and introducing working gas to carry out evacuation treatment on the reactor; b. keeping the continuous introduction of working gas, and treating for 20-50 min under the conditions that the voltage of a plasma reactor is 80-140V and the current is 1.35-1.93A to obtain an oxygen defect nano titanium dioxide catalyst; wherein the working gas is selected from H2And N2And (4) forming. The preparation method is simple, and the prepared catalyst is used for catalyzing and degrading organic mattersThe activity is good.
Description
Technical Field
The invention belongs to the field of synthesis of titanium dioxide photocatalytic materials, and particularly relates to an oxygen-deficient titanium dioxide catalyst and a preparation method and application thereof.
Background
Titanium dioxide photocatalysis has led to extensive research by numerous researchers since Fujishima and Honda (A Fujishima, Honda K. electrochemolysis of water at a semiconductor electrode [ J ] Nature,1972,238(5358):37-38.) found that titanium dioxide single crystal electrodes can decompose water to hydrogen and oxygen under irradiation of ultraviolet light (Honda-Fujishima Effect); because of the advantages of low titanium dioxide price, no toxicity, large ultraviolet response and environmental reserves, etc., the titanium dioxide is widely used in the aspects of organic matter degradation, solar cells, hydrolytic hydrogen production, biotechnology, etc. in recent decades. However, the catalytic application of titanium dioxide under visible light is limited by the defects of wider self forbidden band (3.2ev), high electron hole recombination rate, response only under ultraviolet light (ultraviolet light only accounts for 5% of sunlight) and the like of titanium dioxide, so that the preparation of the titanium dioxide catalyst with high visible light response and high visible light catalytic performance becomes the direction of common efforts of numerous scientists and scholars.
Many scholars for modifying titanium dioxide propose the capabilities of improving catalytic response under visible light, such as element doping, heterojunction, size effect, morphology effect, confinement effect, crystal face effect, defect effect and the like. It has been reported that defects on the surface of titanium dioxide can act as traps for photo-induced charges (Fei Han, Mao Xin, Xu Qing-Hua. Flower-like Au/Ag/TiO 2 nanocompatibilites with enhanced photo-catalytic reactivity [ J Han, Mao Xin, Xu-Xu, Xu-Hua. Flower-like Au/Ag/TiO 2 nanocompatibilites with enhanced photo-catalytic reactivity [ J Han, J]Science China,2017,60(4): 521-. In the preparation of a composition containing defects and Ti3+The process of self-doping titanium dioxide usually adopts element doping and high-temperature calcining methods, and the methods are usually complex in process and high in energy consumption in the preparation process, and are not beneficial to realizationAnd (4) industrial application.
Plasma is a fourth state of matter, plasma is an ionized gaseous matter consisting of atoms after partial electrons are deprived and positive and negative electrons generated after the atoms are ionized, high-energy activated gas in a plasma state has a surface etching function (Zhaobai radio frequency plasma ammonia synthesis and dynamics research [ D ] 2013.), therefore, plasma has been widely applied to the chemical field as a research hotspot in recent years, and partial scholars have developed researches on the role of plasma in modifying titanium dioxide. At present, the development of a titanium dioxide modification method which has the advantages of simple preparation process, easy operation, low production cost, high catalytic activity and easy realization of industrial application is urgently needed.
Therefore, it is an urgent problem to develop a titanium dioxide catalyst having high activity, simple preparation method and suitability for industrial mass production.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of the oxygen-deficient titanium dioxide catalyst, which is simple in preparation method.
A method for preparing an oxygen deficient titanium dioxide catalyst comprising the steps of:
a. uniformly dispersing titanium dioxide in a plasma reactor, and introducing working gas to carry out evacuation treatment on the reactor;
b. keeping the continuous introduction of working gas, and treating for 20-50 min under the conditions that the voltage of a plasma reactor is 80-140V and the current is 1.35-1.93A to obtain an oxygen defect nano titanium dioxide catalyst;
wherein the working gas is selected from H2And N2And (4) forming.
Preferably, the titanium dioxide is nano titanium dioxide; more preferably, the titanium dioxide is P25 type nano titanium dioxide.
Preferably, in steps a and b: the flow rate of the working gas is 40-100 mL/min; more preferably, the flow rate of the working gas is 80-100 mL/min; most preferably, the flow rate of the working gas is 80 mL/min.
Preferably, the working gas consists of H2And N21-60 percent by volume and 99-40 percent by volume; more preferably, the working gas consists of H2And N21-40 percent by volume and 99-60 percent by volume; more preferably: the working gas is composed of H2And N25-10 percent by volume and 95-90 percent by volume; most preferably, H2And N2The weight percentage is 10% to 90%.
Preferably, in step b: the voltage is 100-140V, and the current is 1.58-1.93A; more preferably, the voltage is 100V and the current is 1.58A.
Preferably, the composition and flow rate of the working gas used in step a and the working gas used in step b are the same.
Preferably, the plasma reactor is a DBD dielectric barrier discharge cold plasma generator.
Preferably, in the step b, the treatment time is 20-30 min; preferably, the treatment time is 30 min.
The invention also provides an oxygen deficient titanium dioxide.
The oxygen-deficient titanium dioxide catalyst is prepared by the preparation method of the oxygen-deficient titanium dioxide catalyst.
The invention also provides the use of an oxygen deficient titanium dioxide catalyst.
The oxygen deficient titanium dioxide catalyst is useful for degrading organic contaminants. Preferably, the organic contaminant is methylene blue.
The invention has the beneficial effects that:
1. the invention does not need any other complicated steps and chemical reagents except titanium dioxide and working gas in the experimental process, has novel technology, simple and environment-friendly preparation process, no secondary pollution and low experimental energy consumption.
2. The invention adopts the cold plasma technology to really realize the one-step rapid preparation of the Ti and the oxygen-containing defects3+The self-doped titanium dioxide catalyst with high catalytic activity has wide application range, and the raw materials do not need to be self-madeThe application prospect of (1).
3. The product prepared by the method can be used for degrading organic matters, particularly methylene blue, and the degradation rate reaches more than 77%.
4. The oxygen-deficient titanium dioxide catalyst prepared by the method can be recycled and reused, and still has a high degradation rate.
Drawings
FIG. 1 is a graph of oxygen deficient titanium dioxide prepared in example 5 of the present invention with P25-TiO2XRD spectrum of (1);
FIG. 2 is a graph of oxygen deficient titanium dioxide prepared in example 5 of the present invention with P25-TiO2XPS-O spectrum of (A);
FIG. 3 is a graph of oxygen deficient titanium dioxide prepared in example 5 of the present invention with P25-TiO2XPS-Ti spectrograms of (A);
FIG. 4 is a graph of oxygen deficient titanium dioxide and P25-TiO prepared in example 5 of the present invention2Ultraviolet diffuse reflectance spectrum of (a);
FIG. 5 is a graph of oxygen deficient titanium dioxide and P25-TiO prepared in example 5 of the present invention2The fluorescence spectrum of (a);
FIG. 6 is a graph of oxygen deficient titanium dioxide and P25-TiO prepared in example 5 of the present invention2Comparative photocatalytic performance of (a).
FIG. 7 is a graph showing the photocatalytic performance of oxygen deficient titanium dioxide produced in example 5 of the present invention after being reused three times.
Detailed Description
The preparation method of the oxygen-deficient titanium dioxide catalyst comprises the following steps:
a. uniformly dispersing titanium dioxide in a plasma reactor, and introducing working gas to carry out evacuation treatment on the reactor;
b. keeping the continuous introduction of working gas, then opening a power supply of the plasma reactor, adjusting the voltage and current of the power supply to be in a stable working state, treating for 20-50 min under the conditions that the voltage of the plasma reactor is 80-140V and the current is 1.35-1.93A, closing the power supply after the treatment is finished, then closing a gas source, and cooling the reactor to room temperature to obtain the oxygen defect nano titanium dioxide catalyst;
wherein the working gas is selected from H2And N2And (4) forming.
The reaction of the invention is carried out under normal pressure, and the outside of the reaction does not need to be heated.
Preferably, 0.3 to 0.6g of titanium dioxide is placed in the plasma reactor.
The working gas of the present invention needs to be H2And N2Composition, lack of one can not; the titanium dioxide treated by nitrogen can form nitrogen doping in the surface of the titanium dioxide, the forbidden bandwidth is reduced, the photocatalytic performance is improved, the oxygen defects can be formed on the surface of the titanium dioxide by hydrogen treatment, the formed defects can play a role in capturing photoproduction electrons, the recombination of photoproduction electron pairs is inhibited, the photocatalytic performance is improved, and the titanium dioxide treated by the nitrogen and the titanium dioxide have synergistic effect.
The invention treats titanium dioxide by nitrogen-hydrogen cold plasma atmosphere to form oxygen defects and Ti on the surface of the titanium dioxide3+In the presence of oxygen deficiency and Ti3+Under the combined action of the titanium dioxide valence band and the conduction band, a new defect energy level Ti is formed between the titanium dioxide valence band and the conduction band3 +-Ov-Ti3+The defect energy level plays roles in enhancing the light absorption of the titanium dioxide in a visible light region, promoting the transfer of photo-generated electrons to the surface of the titanium dioxide and prolonging the service life of the photo-generated electrons. Finally, the titanium dioxide catalyst containing the oxygen defect structure has high catalytic activity to methylene blue.
The invention needs to control the voltage to be 80-140V, the voltage is lower than 80V and can not form plasma, and the voltage is higher than 140V and influences the stability of a plasma instrument.
In order to improve the catalytic activity of the prepared titanium dioxide catalyst containing the oxygen defect structure, preferably, the titanium dioxide is nano titanium dioxide; preferably, the titanium dioxide is P25 type nano titanium dioxide. The P25 nanometer titanium dioxide can be directly purchased. The average particle size of the P25 type nano titanium dioxide is 20 nm.
In order to increase the catalytic activity of the produced titanium dioxide catalyst containing oxygen defect structures, it is preferable that in steps a and b: the flow rate of the working gas is 40-100 mL/min; more preferably, the flow rate of the working gas is 80-100 mL/min; most preferably, the flow rate of the working gas is 80 mL/min.
In order to increase the catalytic activity of the produced titanium dioxide catalyst containing oxygen defect structures, it is preferred that the working gas consists of H2And N21-60 percent by volume and 99-40 percent by volume; more preferably, the working gas consists of H2And N21-40 percent by volume and 99-60 percent by volume; further preferably, the working gas is composed of H2And N2According to the volume percentage, the components are 5-10 percent and 90-95 percent; most preferably, H2And N2The weight percentage is 10% to 90%.
In order to increase the catalytic activity of the produced titanium dioxide catalyst containing oxygen defect structures, it is preferable that, in step b: the voltage is 100-140V, and the current is 1.58-1.93A; more preferably, the voltage is 100V and the current is 1.58A.
In order to improve the catalytic activity of the prepared titanium dioxide catalyst containing oxygen defect structure, the composition and flow rate of the working gas used in the step a and the working gas used in the step b are preferably the same.
Preferably, the plasma reactor is a DBD dielectric barrier discharge cold plasma generator.
In order to improve the catalytic activity of the prepared titanium dioxide catalyst containing the oxygen defect structure, preferably, in the step b, the treatment time is 20-30 min; preferably, the treatment time is 30 min.
The invention also provides an oxygen deficient titanium dioxide. The oxygen-deficient titanium dioxide catalyst prepared by the invention has high catalytic activity.
The oxygen-deficient titanium dioxide catalyst is prepared by the preparation method of the oxygen-deficient titanium dioxide catalyst.
The oxygen deficient titanium dioxide catalyst of the present invention is useful for degrading organic pollutants. Preferably, the organic contaminant is methylene blue.
The oxygen-deficient titanium dioxide prepared by the invention can be reused. The using method comprises the following steps: and taking out the used titanium dioxide with oxygen deficiency, washing the precipitate with deionized water for at least three times, and drying overnight to be continuously used. Preferably, the used oxygen-deficient titanium dioxide is taken out in a centrifugal mode, and the drying temperature is 50-70 ℃; more preferably, the drying temperature is 60 ℃.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
In the examples of the present invention and the test examples, the commercial titanium dioxide P25 was used in exactly the same manner.
The oxygen deficient titanium dioxide produced was used to degrade methylene blue in the following tests as described in examples 1-6, and the experimental procedures were as follows:
0.1mg of the prepared product is uniformly dispersed in 50mL of methylene blue solution with the concentration of 100mg/L and irradiated by a 100W xenon lamp. After 2h, a sample was taken for analysis, and the absorbance of methylene blue was measured with a UV spectrophotometer at a maximum absorption wavelength λ max of 664 nm. The degradation rate calculation formula is as follows: d ═ A0-At)/A0]X is 100%; wherein D is the degradation rate, A0The absorbance of the sample before illumination; a. thetThe absorbance of the sample at a light irradiation time of 2 hours.
Example 1
Step 1: uniformly dispersing 0.3g of weighed commercial titanium dioxide P25 in a DBD dielectric barrier discharge cold plasma reactor;
step 2: introducing N into the plasma reactor in the step 12-H2A mixed gas for evacuating air from the plasma reactor in the step 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen is 40mL/min, and N is2:H2The volume percentage is 99 percent to 1 percent, and the emptying time is 5 min;
and step 3: hold N2-H2And (3) continuously introducing in the state of the step 2, then opening a power supply of the DBD cold plasma reactor, and adjusting the voltage and the current of the power supply to be in a stable working state, wherein the voltage is 100V and the current is 1.58A.
And 4, step 4: in step 3 for N2-H2And treating for 30min in a plasma gas atmosphere.
And 5: and after the treatment is finished, firstly, turning off the power supply, then, turning off the gas source, and collecting the catalyst after the reactor is cooled to the room temperature.
Step 6: the oxygen-deficient titanium dioxide photocatalyst prepared in the embodiment is used for degrading 100mg/L methylene blue, and the degradation rate is 82% through tests.
Example 2
Step 1: a weighed amount of 0.3g of commercial titanium dioxide P25 was uniformly dispersed in a DBD dielectric barrier discharge cold plasma reactor.
Step 2: introducing N into the plasma reactor in the step 12-H2A mixed gas for evacuating air from the plasma reactor in the step 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen is 100mL/min, and N is2:H2The volume percentage is 95 percent to 5 percent, and the emptying time is 5 min.
And step 3: hold N2-H2And (3) continuously introducing in the state of the step 2, then opening a power supply of the DBD cold plasma reactor, and adjusting the voltage and the current of the power supply to be in a stable working state, wherein the voltage is 100V and the current is 1.58A.
And 4, step 4: in step 3 for N2-H2And treating the titanium dioxide for 30min in the plasma gas atmosphere.
And 5: and after the treatment is finished, firstly, turning off the power supply, then, turning off the gas source, and collecting the catalyst after the reactor is cooled to the room temperature.
Step 6: the oxygen-deficient titanium dioxide photocatalyst prepared in the embodiment is used for degrading 100mg/L methylene blue, and the degradation rate is 86% by testing.
Example 3
Step 1: a weighed amount of 0.3g of commercial titanium dioxide P25 was uniformly dispersed in a DBD dielectric barrier discharge cold plasma reactor.
Step 2: introducing N into the plasma reactor in the step 12-H2Mixed gas for evacuating air from the plasma reactor in step 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen is80mL/min，N2:H2The volume percentage is 95 percent to 5 percent, and the emptying time is 5 min.
And step 3: hold N2-H2And (3) continuously introducing in the state of the step (2), then opening a power supply of the DBD cold plasma reactor, and adjusting the voltage and the current of the power supply to be in a stable working state, wherein the voltage is 80V and the current is 1.35A.
And 4, step 4: in step 3 for N2-H2And treating the titanium dioxide for 30min in the plasma gas atmosphere.
And 5: and after the treatment is finished, firstly, turning off the power supply, then, turning off the gas source, and collecting the catalyst after the reactor is cooled to the room temperature.
Step 6: the oxygen-deficient titanium dioxide photocatalyst prepared in the embodiment is used for degrading 100mg/L methylene blue, and the degradation rate is 77% by testing.
Example 4
Step 1: a weighed amount of 0.3g of commercial titanium dioxide P25 was uniformly dispersed in a DBD dielectric barrier discharge cold plasma reactor.
Step 2: introducing N into the plasma reactor in the step 12-H2Mixed gas for evacuating air from the plasma reactor in step 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen is 80mL/min, and N is2:H2The volume percentage is 60 percent to 40 percent, and the emptying time is 5 min.
And step 3: hold N2-H2And (3) continuously introducing in the state of the step 2, then opening a power supply of the DBD cold plasma reactor, and adjusting the voltage and the current of the power supply to be in a stable working state, wherein the voltage is 140V and the current is 1.93A.
And 4, step 4: in step 3 for N2-H2And treating the titanium dioxide for 20min in the plasma gas atmosphere.
And 5: and after the treatment is finished, firstly, turning off the power supply, then, turning off the gas source, and collecting the catalyst after the reactor is cooled to the room temperature.
Step 6: the oxygen-deficient titanium dioxide photocatalyst prepared in the embodiment is used for degrading 100mg/L methylene blue, and the degradation rate is 80% by testing.
Example 5
Step 1: a weighed amount of 0.3g of commercial titanium dioxide P25 was uniformly dispersed in a DBD dielectric barrier discharge cold plasma reactor.
Step 2: introducing N into the plasma reactor in the step 12-H2Mixed gas for evacuating air from the plasma reactor in step 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen is 80mL/min, and N is2:H2The volume percentage is 90 percent to 10 percent, and the emptying time is 5 min.
And step 3: hold N2-H2And (3) continuously introducing in the state of the step 2, then turning on a power supply of the DBD cold plasma reactor, and adjusting the voltage and the current of the power supply to be in a stable working state, wherein the voltage is preferably 100V, and the current is preferably 1.58A.
And 4, step 4: in step 3 for N2-H2Under the plasma gas atmosphere, the time for treating the titanium dioxide in the step 4 is preferably 30 min.
And 5: and after the treatment is finished, firstly, turning off the power supply, then, turning off the gas source, and collecting the catalyst after the reactor is cooled to the room temperature.
Step 6: the oxygen-deficient titanium dioxide photocatalyst prepared in the embodiment is used for degrading 100mg/L methylene blue, and the degradation rate is 96% through tests.
The oxygen deficient titanium dioxide produced in this example was tested.
Wherein FIG. 1 shows the oxygen deficient titanium dioxide and P25-TiO prepared in this example2The XRD spectrum of the sample shows that the sample is titanium dioxide after plasma treatment.
FIG. 2 shows the oxygen deficient titanium dioxide prepared in this example with P25-TiO2FIG. 3 is an XPS-O spectrum of the oxygen deficient titanium dioxide prepared in this example with P25-TiO2From the XPS-Ti spectrograms of FIGS. 2 and 3, it can be seen that oxygen defects and Ti are generated after plasma treatment of P25 titanium dioxide3+。
FIG. 4 shows the oxygen deficient titanium dioxide and P25-TiO prepared in this example2The ultraviolet diffuse reflectance spectrum of (A) shows that the dioxide is present after plasma treatment of P25The titanium oxide is red-shifted in the visible light region, which is favorable for the photocatalytic reaction.
FIG. 5 shows the oxygen deficient titanium dioxide and P25-TiO prepared in this example2The fluorescence spectrum of the titanium dioxide shows that the fluorescence intensity of the P25 titanium dioxide after plasma treatment is weakened, which indicates that the recombination of photo-generated electron-hole pairs is inhibited.
Example 6
Step 1: a weighed amount of 0.3g of commercial titanium dioxide P25 was uniformly dispersed in a DBD dielectric barrier discharge cold plasma reactor.
Step 2: introducing N into the plasma reactor in the step 12-H2Mixed gas for evacuating air from the plasma reactor in step 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen is 80mL/min, and N is2:H2The volume percentage is 95 percent to 5 percent, and the emptying time is 5 min.
And step 3: hold N2-H2And (3) continuously introducing in the state of the step 2, then opening a power supply of the DBD cold plasma reactor, and adjusting the voltage and the current of the power supply to be in a stable working state, wherein the voltage is 140V and the current is 1.93A.
And 4, step 4: in step 3 for N2-H2Under the plasma gas atmosphere, the time for treating the titanium dioxide is preferably 50 min.
And 5: and after the treatment is finished, firstly, turning off the power supply, then, turning off the gas source, and collecting the catalyst after the reactor is cooled to the room temperature.
Step 6: the oxygen-deficient titanium dioxide photocatalyst prepared in the embodiment is used for degrading 100mg/L methylene blue, and the degradation rate is 84% through tests.
Test example 1
The oxygen deficient titanium dioxide prepared in example 5 was used to degrade 100mg/L of methylene blue and the rate of degradation of methylene blue was measured at various times.
P25 titanium dioxide without any treatment was used to degrade 100mg/L of methylene blue, and the degradation rate of methylene blue was measured at different times.
The test method comprises the following steps: taking 0.1mg of the product to be uniformly dispersed in 50mLA methylene blue solution having a concentration of 100mg/L was irradiated with a 100W xenon lamp. And (4) sampling and analyzing after t min, and detecting the absorbance of methylene blue by using an ultraviolet spectrophotometer at the position of the maximum absorption wavelength lambda max which is 664 nm. The degradation rate calculation formula is as follows: d ═ A0-At)/A0]X is 100%; wherein D is the degradation rate, A0The absorbance of the sample before illumination; a. thetThe absorbance of the sample at the time of light irradiation for t min.
The results are shown in table 1 below and fig. 6.
TABLE 1
| 20min | 40min | 60min | 80min | 100min | 120min | |
| Example 5 | 40％ | 64％ | 83％ | 89％ | 92％ | 96％ |
| |
10％ | 23％ | 33％ | 42％ | 52％ | 58％ |
It can be seen that the photocatalytic performance of the P25 titanium dioxide after plasma treatment is greatly improved, and is consistent with the characterization results.
Test example 2
Centrifuging the oxygen-deficient titanium dioxide used in the step 6 in the example 5, taking out, washing the precipitate with deionized water for three times, drying at 60 ℃ overnight, degrading 100mg/L methylene blue, and testing the degradation rate of the first-time repeated process; centrifuging the used titanium dioxide with oxygen deficiency, taking out the titanium dioxide, washing the precipitate with deionized water for three times, drying the precipitate at 60 ℃ overnight, degrading 100mg/L methylene blue, and testing the degradation rate of the titanium dioxide after the second repetition; and then taking out the used oxygen-deficient titanium dioxide by centrifugation, washing the precipitate with deionized water for three times, drying the precipitate at 60 ℃ overnight, degrading 100mg/L methylene blue, and testing the degradation of the precipitate after the third repetition.
The test method was the same as in test example 1. The results of each repetition are shown in table 3 and fig. 7.
TABLE 3
| 20min | 40min | 60min | 80min | 100min | 120min | |
| First repetition | 86％ | 88％ | 89％ | 91％ | 91％ | 91％ |
| Second repetition | 87％ | 92％ | 96％ | 97％ | 98％ | 98％ |
| Third repetition | 89％ | 95％ | 98％ | 99％ | 99％ | 99％ |
As can be seen generally in fig. 7 and table 3, the post-regeneration catalytic performance is higher than the first use.
Claims (10)
1. The preparation method of the oxygen-deficient titanium dioxide catalyst is characterized by comprising the following steps of:
a. uniformly dispersing titanium dioxide in a plasma reactor, and introducing working gas to carry out evacuation treatment on the reactor;
b. keeping the continuous introduction of working gas, and treating for 20-50 min under the conditions that the voltage of a plasma reactor is 80-140V and the current is 1.35-1.93A to obtain an oxygen defect nano titanium dioxide catalyst;
wherein the working gas is selected from H2And N2And (4) forming.
2. The method for producing an oxygen-deficient titanium dioxide catalyst according to claim 1, wherein in the step a, the titanium dioxide is nano titanium dioxide; preferably, the titanium dioxide is P25 type nano titanium dioxide.
3. The method for producing an oxygen-deficient titanium dioxide catalyst according to claim 1, wherein in steps a and b: the flow rate of the working gas is 40-100 mL/min; preferably, the flow rate of the working gas is 80-100 mL/min; more preferably, the flow rate of the working gas is 80 mL/min.
4. The method for producing an oxygen-deficient titanium dioxide catalyst according to any one of claims 1 to 3 wherein the working gas is composed of H2And N21-60 percent by volume and 99-40 percent by volume; preferably, the working gas consists of H2And N21-40 percent by volume and 99-60 percent by volume; more preferably, the working gas consists of H2And N25-10 percent by volume and 95-90 percent by volume; further preferably, H2And N2The weight percentage is 10% to 90%.
5. The method for producing an oxygen-deficient titanium dioxide catalyst according to any one of claims 1 to 4, wherein in step b: the voltage is 100-140V, and the current is 1.58-1.93A; preferably, the voltage is 100V and the current is 1.58A.
6. The method of producing an oxygen-deficient titania catalyst according to claim 1 wherein the working gas used in step a is the same as the working gas used in step b in composition and flow rate.
7. The method of preparing an oxygen-deficient titanium dioxide catalyst according to claim 1 wherein the plasma reactor is a DBD dielectric barrier discharge cold plasma generator.
8. The method for preparing an oxygen-deficient titanium dioxide catalyst according to any one of claims 1 to 7, wherein in the step b, the treatment time is 20 to 30 min; preferably, the treatment time is 30 min.
9. An oxygen-deficient titanium dioxide catalyst, characterized by being produced by the production method of an oxygen-deficient titanium dioxide catalyst according to any one of claims 1 to 8.
10. Use of the oxygen deficient titanium dioxide catalyst according to claim 9 wherein the oxygen deficient titanium dioxide catalyst is used for the degradation of organic contaminants; preferably, the organic contaminant is methylene blue.
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