CN115212864A - Method for improving visible light response of photocatalyst material by oxygen vacancy defect synergistic passivation effect - Google Patents
Method for improving visible light response of photocatalyst material by oxygen vacancy defect synergistic passivation effect Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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Abstract
The invention belongs to the technical field of new materials and photocatalytic degradation, and discloses an oxygen vacancy defect synergistic passivation effectVisible light response method of high photocatalyst material, and oxygen vacancy defect layer and Al constructed by combining atomic layer deposition method and plasma vapor deposition method 2 O 3 An active surface interface of (a); the method comprises the steps of preparing the ultra-small titanium dioxide with an anatase phase by a sol-gel method, and modifying the surface of the ultra-small titanium dioxide by an ALD-plasma combined technology. The invention utilizes ALD-plasma combined technology to construct an oxygen vacancy defect layer and Al 2 O 3 The active surface interface of (2) enables the composite center of the surface part of the titanium dioxide to be passivated, and the specific surface area of the material is enlarged; al (Al) 2 O 3 The porous structure formed by deposition is beneficial to electron transmission, enhances the separation and diffusion of photon-generated carriers, improves the photocatalytic adsorption and activation reaction on the surface of the material, and is practically effective when applied to the fields of environmental protection and photodegradation of organic pollutants.
Description
Technical Field
The invention belongs to the technical field of new materials and photocatalytic degradation, and particularly relates to a method for improving visible light response of a photocatalyst material by virtue of an oxygen vacancy defect synergistic passivation effect.
Background
At present, the photocatalysis technology has great development potential in the aspect of providing clean energy as a green technology for converting solar energy into chemical energy. Titanium dioxide (TiO) 2 ) Has gained wide attention as the best overall performance photocatalytic material. But TiO 2 2 The existence of a large number of oxygen vacancy defects on the surface of the material is not favorable for carrier separation and transport, or the defects become recombination centers to cause photon-generated carrier recombination, so that the photocatalytic activity is reduced, the catalytic reaction is hindered, and the application of the material in actual life is limited. On the other hand, the surface state of the nanostructure is particularly important for the charge recombination velocity and the catalytic reaction, the method commonly used for passivating the surface state is surface coating, and the ALD process, as a powerful technology for constructing a passivation layer, has the excellent advantages of remarkable control interface, remarkable uniformity, accurate thickness control and the like. Currently, a large number of materials are prepared by ALD processes, such as some Al 2 O 3 、SiO 2 And Fe 3 O 4 And the like. And secondly, the introduction of the passivation layer can effectively passivate the crystal boundary defect of the composite structure, reduce the bulk phase recombination of photon-generated carriers and reduce the recombination rate of surface carriers, thereby realizing the enhancement of the photocatalytic performance.
Through the above analysis, the problems and defects of the prior art are as follows: the existence of a large number of oxygen vacancy defects on the surface of the titanium dioxide material is not favorable for carrier separation and transportation, or the defects become recombination centers to cause photon-generated carrier recombination, so that the photocatalytic activity is reduced, the catalytic reaction is hindered, and the application of the titanium dioxide material in actual life is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for improving the visible light response of a photocatalyst material by the synergistic passivation effect of oxygen vacancy defects, and particularly relates to a method for improving the photocatalytic activity of a titanium dioxide material by the synergistic effect of defect engineering and passivation.
The invention is realized in such a way that the method for improving the visible light response of the photocatalyst material by the synergistic passivation effect of the oxygen vacancy defects comprises the following steps:
method for constructing oxygen vacancy defect layer and Al by combining atomic layer deposition method and plasma vapor deposition method 2 O 3 An active surface interface of (a); the method comprises the steps of preparing ultra-small titanium dioxide with an anatase phase by a sol-gel method, and modifying the surface of the ultra-small titanium dioxide by an ALD-plasma combined technology to obtain the photocatalyst material.
Further, the method for improving the visible light response of the photocatalyst material by the oxygen vacancy defect synergistic passivation effect comprises the following steps:
weighing titanium dioxide, placing the titanium dioxide in a cavity of a tubular furnace device, and introducing inert gas; starting a vacuum pump, carrying out vacuum pumping treatment on the cavity of the tube furnace, and keeping continuous introduction of inert gas;
starting a plasma excitation source to perform plasma induction treatment, and keeping the continuous introduction of inert gas; after the reaction is finished, plasma-induced modified titanium dioxide is obtained;
step three, weighing plasma induced modified titanium dioxide, uniformly placing the titanium dioxide in a circular tray, and placing the titanium dioxide in the center of an ALD (atomic layer deposition) experiment cavity; opening circulating cooling water, and introducing nitrogen;
starting a vacuum pump, and vacuumizing the cavity of the tubular furnace to enable the reaction cavity to reach a vacuum environment; selecting trimethylaluminum as an aluminum source and deionized water as an oxygen source, and performing an ALD (atomic layer deposition) procedure;
step five, weighing titanium dioxide, uniformly placing the titanium dioxide in a circular tray, and placing the titanium dioxide in the center of an ALD experiment cavity; opening circulating cooling water, introducing nitrogen, and setting flow rate and ALD period;
starting a program, depositing alumina at a certain temperature, and setting a cycle period; and after the reaction is finished, obtaining the composite material of the alumina and the titanium dioxide.
Further, the weighing amount of the titanium dioxide in the step one is 0.2-1 g; the total flow rate of the inert gas is 20-100 mL/min, and the time of the inert gas is 10-20 min.
Further, in the first step, starting a vacuum pump to perform vacuum pumping treatment, so that the vacuum degree in the cavity is maintained within the range of 10-100 Pa; the flow rate of the inert gas is 50mL/min, and the temperature in the furnace is kept between 20 and 30 ℃.
Further, in the second step, plasma induction treatment is carried out for 5-20 min under the power of 100-200W, and the flow rate of the inert gas is 50mL/min.
Further, the weighed amount of the plasma-induced modified titanium dioxide in the third step is 0.2-1 g, and the diameter of the circular tray is 4cm.
Further, the weighing amount of the titanium dioxide in the fifth step is 0.2-1 g, the diameter of the circular tray is 4cm, and the flow rate of the introduced nitrogen is 20sccm; the ALD cycle is set to: h 2 10ms for O pulse, 10ms for TMA pulse, H 2 O pulses for 10ms.
Further, in the sixth step, the deposition of alumina is carried out at a temperature of 100-200 ℃, and the cycle period is set to 10-100 cycles.
The invention also aims to provide a sandwich structure photocatalyst material with visible light response, which is prepared by implementing the method for improving the visible light response of the photocatalyst material by the oxygen vacancy defect synergistic passivation effect.
The invention also aims to provide an application of the sandwich structure photocatalyst material with visible light response in degrading rhodamine B organic dye as a photocatalyst.
In combination with the above technical solutions and the technical problems to be solved, please analyze the advantages and positive effects of the technical solutions to be protected in the present invention from the following aspects:
first, aiming at the technical problems existing in the prior art and the difficulty in solving the problems, the technical problems to be solved by the technical scheme of the present invention are closely combined with the technical scheme to be protected and the results and data in the research and development process, and some creative technical effects brought after the problems are solved are analyzed in detail and deeply. The specific description is as follows:
the invention provides a method for improving visible light response of a photocatalyst material by oxygen vacancy defect synergistic passivation, which combines an Atomic Layer Deposition (ALD) method and a plasma vapor deposition method to construct an oxygen vacancy defect layer and Al 2 O 3 Active surface interface of (2). The invention prepares the ultra-small titanium dioxide with anatase phase by a sol-gel method; and modifying the surface of the ultra-small titanium dioxide by using an ALD-plasma combined technology. Compared with the traditional preparation process, the preparation method has the advantages that the process is simple, the grain size is 2-10 nm, the rhodamine B organic dye can be rapidly degraded within 12min under the drive of low-power visible light, and the excellent photocatalytic activity and stability are shown; meanwhile, the band gap is narrowed to 2.38eV, and the visible light response range is expanded.
The invention relates to a method for synergistically enhancing the photocatalytic activity of a titanium dioxide material by defect engineering and passivation effects, and a modified composite material is used as a photocatalyst material to degrade rhodamine B organic dye.
The invention prepares the modifiedThe titanium dioxide is realized by using an ALD-plasma combined technology, the surface modification of the titanium dioxide can be effectively realized by controlling the process conditions, the active surface is constructed, the response of visible light is enhanced, and the mass transfer capacity of organic pollutants is improved; al of such amorphous structure 2 O 3 The layer can effectively passivate partial composite centers on the surface of the titanium dioxide material, so that the photocatalytic adsorption and activation reactions on the surface of the material are improved; second Al 2 O 3 The porous structure formed by the passivation layer is beneficial to electron transmission to the surface of the material to participate in catalytic reaction, further enhances the separation and diffusion of photon-generated carriers, increases the specific surface area of the material, and provides richer contact area and active sites for reaction. The oxygen vacancy defect layer enabling TiO 2 And Al 2 O 3 The connection is tight, and the device can be used as an electron transmission channel to effectively promote charge conduction.
Secondly, considering the technical scheme as a whole or from the perspective of products, the technical effect and advantages of the technical scheme to be protected by the invention are specifically described as follows:
the invention aims to overcome the defects in the prior art and provides ALD-plasma combined technology surface modified titanium dioxide (TiO) 2 ) The method of (1). The invention utilizes ALD-plasma combined technology to construct an oxygen vacancy defect layer and Al 2 O 3 Active surface of (2), so that titanium dioxide (TiO) 2 ) The surface part is compounded with the center and passivated, so that the specific surface area of the material is enlarged; al (Al) 2 O 3 The porous structure formed by deposition is beneficial to electron transmission, enhances the separation and diffusion of photon-generated carriers, and improves the photocatalytic adsorption and activation reaction on the surface of the material; on the other hand, the catalyst can be used as a protective layer to keep the surface catalytic active sites, thereby being beneficial to long-term use.
The sandwich structure photocatalyst material with visible light response provided by the invention has low band gap, good visible light absorption capacity and excellent photocatalytic activity, is practically and effectively applied to the fields of environmental protection and photodegradation of organic pollutants, and has good application prospect in the field.
Third, as an inventive supplementary proof of the claims of the present invention, there are also presented several important aspects:
(1) The expected income and commercial value after the technical scheme of the invention is converted are as follows:
the invention belongs to the direction of green, environment-friendly and clean energy. The technical scheme can be converted into photocatalyst product development, and plays a positive role in the aspects of purifying air and creating green ecological environment. In the fields of indoor air purification, hospital sterile environment engineering or sterilization of an underwater space closed space, the market value potential is large, and after the technical scheme is converted and implemented, the economic income increase of more than 100 ten thousand is expected to be realized. The method has the advantages that the method has good social benefits in both the expansion of the industry application field and the green sustainable development of the product to the society.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a method for improving visible light response of a photocatalyst material by synergistic passivation of oxygen vacancy defects, according to an embodiment of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image at different magnifications of a modified titanium dioxide provided by an embodiment of the invention;
FIG. 3 is an XRD pattern of a modified titanium dioxide provided by an embodiment of the present invention;
FIG. 4 is a Raman diagram of a modified titanium dioxide provided by an embodiment of the present invention;
FIG. 5 is a FTIR plot of a modified titanium dioxide provided by an embodiment of the present invention;
FIG. 6 is an XPS plot of modified titanium dioxide as provided by an example of the present invention;
FIG. 7 is an absorption spectrum and Tauc-plot of modified titanium dioxide provided in example of the present invention;
FIG. 8 is a rhodamine B degradation performance test chart of the modified titanium dioxide provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a method for improving the visible light response of a photocatalyst material by the synergistic passivation effect of oxygen vacancy defects, and the invention is described in detail below with reference to the accompanying drawings.
1. The embodiments are explained. This section is an explanatory embodiment expanding on the claims so as to fully understand how the present invention is embodied by those skilled in the art.
As shown in fig. 1, the method for improving visible light response of a photocatalyst material by synergistic passivation of oxygen vacancy defects provided by the embodiment of the present invention includes the following steps:
s101, weighing titanium dioxide, placing the titanium dioxide in a cavity of a tubular furnace device, and introducing inert gas; starting a vacuum pump, carrying out vacuum pumping treatment on the cavity of the tube furnace, and keeping continuous introduction of inert gas;
s102, starting a plasma excitation source to perform plasma induction treatment, and keeping continuous introduction of inert gas; after the reaction is finished, plasma-induced modified titanium dioxide is obtained;
s103, weighing plasma induced modified titanium dioxide, uniformly placing the titanium dioxide in a circular tray, and placing the titanium dioxide in the center of an ALD (atomic layer deposition) experiment cavity; opening circulating cooling water, and introducing nitrogen;
s104, starting a vacuum pump, and vacuumizing the cavity of the tube furnace to enable the reaction cavity to reach a vacuum environment; selecting trimethylaluminum as an aluminum source and deionized water as an oxygen source, and performing an ALD (atomic layer deposition) procedure;
s105, weighing titanium dioxide, uniformly placing the titanium dioxide in a circular tray, and placing the circular tray in the center of an ALD experiment cavity; opening circulating cooling water, introducing nitrogen, and setting flow rate and ALD period;
s106, starting a program, depositing aluminum oxide at a certain temperature, and setting a cycle period; and after the reaction is finished, obtaining the composite material of the alumina and the titanium dioxide.
As a preferred embodiment, the method for modifying titanium dioxide by atomic layer deposition provided in the embodiment of the present invention specifically includes the following steps:
step 3, starting a vacuum pump, and vacuumizing the cavity of the tubular furnace to enable the reaction cavity to reach a vacuum environment; simultaneously, trimethylaluminum (TMA) is selected as an aluminum source and deionized water (H) 2 O) is taken as an oxygen source, ALD program setting step 1 is carried out, 0.2-1 g of titanium dioxide is weighed and uniformly placed in a circular tray with the diameter of 4cm, and the circular tray is placed in the center of an ALD experiment cavity; and opening the circulating cooling water, then introducing nitrogen and setting the flow rate of the nitrogen to be 20sccm; then, one ALD cycle is set to: h 2 O pulse (10 ms) -TMA pulse (10 ms) -H 2 O pulse (10 ms).
And 4, starting a program, depositing the alumina at the temperature of 100-200 ℃, wherein the cycle period is 10-100 circles, and obtaining the composite material of the alumina and the titanium dioxide after the reaction is finished.
The invention also provides application of the titanium dioxide modified by the method, and when the titanium dioxide is applied as a photocatalyst, the organic dye rhodamine B can be efficiently degraded under the condition of visible light.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
The method for modifying titanium dioxide by the atomic layer deposition technology comprises the following steps:
and 2, setting the reaction temperature to be 180 ℃, and performing 50-circle circulating deposition at the power of 180 ℃ to obtain a modified titanium dioxide sample which is brown.
The performance of the photodegradable rhodamine B of the sample is tested, and the concentration of the rhodamine B in the solution is suddenly reduced after the rhodamine B is adsorbed in a dark room for 20min, which shows that compared with a P25 material, the modified titanium dioxide material prepared by the invention has higher adsorption effect, and the rhodamine B molecule in the solution is completely degraded after the titanium dioxide material is illuminated for 12 min.
Example 2
Compared with the embodiment 1, the embodiment 2 of the invention has the following differences: the process adjustment of step 2 is: in the step 2, the ALD program reaction temperature is set to be 200 ℃; the rest steps are the same as the steps in the embodiment 1 of the invention, and after the temperature is naturally cooled, the obtained modified titanium dioxide sample is brown.
Example 3
Compared with the embodiment 1, the embodiment 3 of the invention has the following differences: the process of step 2 is adjusted as follows: in step 2, the ALD apparatus was started and the modified titanium dioxide sample was obtained by cyclic deposition for 100 cycles at a temperature of 180 ℃, the obtained sample being brown.
FIG. 2 is a Transmission Electron Microscope (TEM) image of titanium dioxide obtained by the present invention at different magnificationsAn image; FIG. 2 (a) is a TEM image at low magnification of example 1 of the present invention, and it is found that the particle size of the modified sample particles is small and many particles are stacked together; FIG. 2 (b) is a high resolution TEM image of example 1 of the present invention, wherein the modified titania has a particle size of 2 to 5nm, and exhibits (101) crystal planes with a lattice spacing of 0.35nm. Meanwhile, the modified titanium dioxide prepared by the method has an obvious disordered layer on the outer part. Based on the reaction equation for ALD cycle deposition, one can preliminarily conclude that TiO is present 2 The substance with increased surface amorphous region is Al 2 O 3 。
FIG. 3 is an XRD pattern of titanium dioxide obtained in example 1 of the present invention; the figure shows 8 diffraction characteristic peaks corresponding to the (101), (004), (200), (105), (204), (116), (215) and (224) crystal planes, which are associated with anatase phase TiO 2 (PDF-21-127), which also demonstrates Al coating by ALD 2 O 3 The structural composition of the sample before modification is not changed after the layer.
FIG. 4 is a Raman diagram of a modified titanium oxide obtained in example 1 of the present invention; the Raman test range is 150-800 cm -1 The Raman spectra of the titanium dioxide samples before and after modification show four characteristic peaks, corresponding respectively to the anatase TiO 2 E of (A) g ，B 1g 、A 1g And E g 。
FIG. 5 is a FTIR plot of the modified titania obtained in example 1 of the present invention; the infrared spectrum measuring range is 4000-400 cm -1 3419cm for the samples obtained in the untreated and inventive example 1 -1 And 3400cm -1 The characteristic peak at (A) is due to O-H stretching, 1630cm -1 And 1620cm -1 The characteristic peak is caused by physical adsorption of H introduced into the ALD chamber 2 O bending vibration. For titanium dioxide for treatment, at 1000cm -1 The characteristic peak shown by the inner fingerprint area is TiO 2 Bending vibrations of Ti-O-Ti and Ti-O-C in the crystal lattice. Al deposition by ALD 2 O 3 Then, at 500-1000 cm -1 The characteristic infrared peak in the range is broadened because it is at 1000cm -1 Inner fingerprint area Al-O-Al bending vibrationPeaks and Al-O stretching vibration peaks may overlap with Ti-O-Ti and Ti-O-C peaks. FT-IR results further confirm Al 2 O 3 Successfully deposited on the surface of the material.
FIG. 6 is an XPS chart of a modified titanium dioxide obtained by the present invention; the surface chemical state and composition were analyzed by XPS spectroscopy, and the presence of Ti, O, C, and Al elements was clearly indicated, as shown in fig. 6 (a). FIG. 6 (b) is an XPS spectrum of Ti 2p, which is clearly observed to belong to TiO 2 Are each Ti 2p 1/2 And Ti 2p 3/2 . FIG. 6 (C) is the energy spectrum of C1s, and the characteristic peaks at 284.8eV,286.6eV and 289.0eV correspond to C-C bond, C-O bond and Ti-O-C bond, respectively, further illustrating the presence of C doping in the modified sample. Shown in FIG. 6 is (d) an O1s spectrum showing three main characteristic peaks having binding energies of 530.2eV, 531.2eV and 532.4eV, respectively, corresponding to Ti-O-Ti bond, al-O bond and Ti-O-C bond. As shown in FIG. 6 (e), the characteristic peak at 75.0eV in the XPS spectrum of Al 2p corresponds to the Al-O bond. The XPS spectra of O1s with binding energies at 531.2eV and Al 2p with binding energies at 75.0eV demonstrate that Al 2 O 3 Is performed.
FIG. 7 is an absorption spectrum and a Tauc-plot of the modified titanium dioxide obtained in example 1 of the present invention;
FIG. 7 (a) shows that the modified titanium dioxide has a visible light response and an absorption band edge position of 500nm, and thus Al is deposited by the ALD technique 2 O 3 The material of (a) can have an absorption capacity in the visible region; fig. 7 (b) shows that the modified titania has a band gap of 2.38eV.
FIG. 8 is a rhodamine B degradation performance test chart of the modified titanium dioxide obtained in example 1 of the present invention. FIG. 8 (a) is a graph showing the degradation performance of the modified titanium dioxide in the presence of low-power visible light having a wavelength of 450nm for 30 min; after the solution is adsorbed in a dark room for 20min, the concentration of rhodamine B in the solution is reduced by 88 percent; after 12min of illumination, 100% RhB decolorization was achieved. Compared with the commercialized P25 material, the modified titanium dioxide has high adsorption capacity and activation capacity, and the modified titanium dioxide prepared by the method has visible light response. Fig. 8 (b) is a graph of the degradation performance of RhB organic dye contamination under visible light irradiation for 4 consecutive cycles; the good catalytic activity is kept in 4 times of degradation, and the RhB organic pollutants can be completely degraded (100%), so that the material after ALD treatment has excellent stability and catalytic activity in the photocatalytic reaction process.
In conclusion, the material provided by the invention has low band gap, good visible light absorption capacity and excellent photocatalytic activity, is practically effective in the fields of environmental protection and photodegradation of organic pollutants, and has good application prospect in the fields.
2. Application examples. In order to prove the creativity and the technical value of the technical scheme of the invention, the part is the application example of the technical scheme of the claims on specific products or related technologies.
The photocatalyst spraying coating or the air purifying device containing the photocatalyst filter screen is applied to an air purifying system of a submarine, a space capsule and a hospital sterile operating room, and the visible light absorption capacity of the photocatalyst spraying coating or the air purifying device is improved by enhancing the surface adsorption and photo-generated carrier separation capacity of the photocatalyst material, so that the photocatalyst spraying coating or the air purifying device can purify air under the photocatalysis action of a dark room and a weak light condition, and the health of workers in a closed space is ensured.
3. Evidence of the relevant effects of the examples. The embodiment of the invention has some positive effects in the process of research and development or use, and indeed has great advantages compared with the prior art, and the following contents are described by combining data, charts and the like in the test process.
Fig. 7 (a) demonstrates that the photocatalyst material of the present invention has a visible light response, exhibiting enhanced photocatalytic activity, with an absorption band edge expanded to 500nm. The results of fig. 8 (a) show that the photocatalyst material of the present invention achieves 100% decolorization of RhB dye molecules in 12min in the presence of visible light irradiation only, and has higher surface photocatalytic adsorption and activation reaction capacities relative to the commercial P25 material.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for improving the visible light response of a photocatalyst material by the synergistic passivation effect of oxygen vacancy defects is characterized by comprising the following steps:
construction of oxygen vacancy defect layer and Al by combining atomic layer deposition method and plasma vapor deposition method 2 O 3 An active surface interface of (a); the method comprises the steps of preparing ultra-small titanium dioxide with an anatase phase by a sol-gel method, and modifying the surface of the ultra-small titanium dioxide by an ALD-plasma combined technology to obtain the photocatalyst material.
2. The method of claim 1, wherein the method for improving visible light response of photocatalytic material by oxygen vacancy defect synergistic passivation comprises the steps of:
weighing titanium dioxide, placing the titanium dioxide in a cavity of a tubular furnace device, and introducing inert gas; starting a vacuum pump, carrying out vacuum pumping treatment on the cavity of the tube furnace, and keeping continuous introduction of inert gas;
starting a plasma excitation source to perform plasma induction treatment, and keeping the continuous introduction of inert gas; after the reaction is finished, plasma-induced modified titanium dioxide is obtained;
step three, weighing plasma induced modified titanium dioxide, uniformly placing the titanium dioxide in a circular tray, and placing the titanium dioxide in the center of an ALD (atomic layer deposition) experiment cavity; opening circulating cooling water, and introducing nitrogen;
starting a vacuum pump, and vacuumizing the cavity of the tubular furnace to enable the reaction cavity to reach a vacuum environment; selecting trimethylaluminum as an aluminum source and deionized water as an oxygen source, and performing an ALD (atomic layer deposition) procedure;
step five, weighing titanium dioxide, uniformly placing the titanium dioxide in a circular tray, and placing the titanium dioxide in the center of an ALD experiment cavity; opening circulating cooling water, introducing nitrogen, and setting flow rate and ALD period;
starting a program, depositing alumina at a certain temperature, and setting a cycle period; and after the reaction is finished, obtaining the composite material of the alumina and the titanium dioxide.
3. The method for improving the visible light response of the photocatalyst material through the oxygen vacancy defect synergistic passivation effect as claimed in claim 2, wherein the weighed amount of the titanium dioxide in the first step is 0.2-1 g; the total flow rate of the inert gas is 20-100 mL/min, and the time of the inert gas is 10-20 min.
4. The method for improving the visible light response of the photocatalyst material through the oxygen vacancy defect synergistic passivation effect as claimed in claim 2, wherein in the first step, a vacuum pump is started to perform vacuum pumping treatment, so that the vacuum degree in the cavity is maintained within the range of 10-100 Pa; the flow rate of the inert gas is 50mL/min, and the temperature in the furnace is kept between 20 and 30 ℃.
5. The method for improving the visible light response of the photocatalytic material through the oxygen vacancy defect synergistic passivation effect as claimed in claim 2, wherein in the second step, the plasma induction treatment is performed for 5-20 min under the power of 100-200W, and the flow rate of the inert gas is 50mL/min.
6. The method for improving the visible light response of a photocatalyst material through the synergistic passivation effect of oxygen vacancy defects as claimed in claim 2, wherein the weighed amount of the plasma-induced modified titanium dioxide in the third step is 0.2-1 g, and the diameter of the circular tray is 4cm.
7. The method for improving the visible light response of the photocatalyst material through the oxygen vacancy defect synergistic passivation effect as claimed in claim 2, wherein the weighed amount of the titanium dioxide in the fifth step is 0.2-1 g, the diameter of the circular tray is 4cm, and the flow rate of the introduced nitrogen is 20sccm;the ALD cycle is set to: h 2 10ms for O pulse, 10ms for TMA pulse, H 2 O pulses for 10ms.
8. The method for improving the visible light response of a photocatalyst material through the synergistic passivation effect of oxygen vacancy defects as claimed in claim 2, wherein in the sixth step, the deposition of alumina is performed at a temperature of 100-200 ℃, and the cycle period is set to 10-100 cycles.
9. A photocatalyst material with a sandwich structure and visible light response prepared by implementing the method for improving the visible light response of the photocatalyst material by the oxygen vacancy defect synergistic passivation effect of any one of claims 1 to 8.
10. The application of the photocatalyst material with the sandwich structure and the visible light response as claimed in claim 9 in degrading rhodamine B organic dye as a photocatalyst.
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| CN108311131A (en) * | 2017-12-21 | 2018-07-24 | 安徽理工大学 | A kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material and preparation method |
| CN111013560A (en) * | 2019-12-26 | 2020-04-17 | 西南石油大学 | Oxygen-deficient titanium dioxide catalyst, preparation method and application thereof |
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