CN114849733A - Application of nanotube array in preparation of photocatalytic material - Google Patents
Application of nanotube array in preparation of photocatalytic material Download PDFInfo
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Abstract
The invention discloses an application of a nanotube array in preparing a photocatalytic material, which comprises titanium sheet pretreatment; calcining the titanium dioxide nanotube; respectively soaking the titanium dioxide nanotubes in AgNO 3 Solution, Na 2 S and Cdcl 2 Obtaining a photocatalytic material in the solution; wherein, the AgNO 3 The concentration of the solution is 0.02-0.2 mol/L; the Na is 2 The concentration of S is 0.1-0.2 mol/L, and the Cdcl 2 The concentration of the solution is 0.1-0.2 mol/L.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to an application of a nanotube array in preparation of a photocatalytic material.
Background
TiO 2 The photocatalytic performance of the material is discovered only in 1972, and the research focus is mainly on how to utilize the material to create more materials and values for people. Because the environment situation of the 21 st century is severe, the fog in the air frequently occurs, the water pollution frequently becomes urgent, and the like, the photocatalytic degradation is regarded as TiO 2 The most potential uses of the material. TiO 2 2 The material can degrade most organic pollutants in gas and liquid, and is particularly applied to substances which are difficult to degrade in common materials, such as degradation of dyes commonly used in textile dyeing and finishing, degradation of toxic substances such as nitric oxide in air and the like, degradation of toxic organic matters in water, and degradation final products are harmless salts such as carbon dioxide, water and the like, so that the material has great prospect in the aspect of product cleaning. With the development of scientific technology, the degradation time can be shortened greatly.
When light irradiates the surface of a semiconductor, only light quanta with relatively strong energy can play a role, because only the wavelength of the light is short enough to prevent conduction band electrons and valence band holes from being recombined, and the light can not be released in the form of heat energy or other forms. The semiconductor anatase type has a forbidden band width of 3.2eV, that is, only light with a wavelength less than 387.5nm irradiates the TiO 2 The surface of the semiconductor material can make the electrons on the surface of the semiconductor material transit. It has been attempted to coat a large number of materials, such as semiconductors with narrower gap bands, on TiO 2 The nanotube surface is used for further improving the performance and increasing the photoelectrochemical activity of a visible light region.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
As one aspect of the invention, the invention provides an application of a nanotube array in preparing a photocatalytic material.
In order to solve the technical problems, the invention provides the following technical scheme: an application of a nanotube array in preparing a photocatalytic material comprises,
pretreating a titanium sheet;
calcining the titanium dioxide nanotube;
respectively soaking the titanium dioxide nanotubes in AgNO 3 Solution, Na 2 S and Cdcl 2 Obtaining a photocatalytic material in the solution;
wherein, the AgNO 3 The concentration of the solution is 0.02-0.2 mol/L; the Na is 2 The concentration of S is 0.1-0.2 mol/L, and the Cdcl 2 The concentration of the solution is 0.1-0.2 mol/L.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the titanium sheet is pretreated by ultrasonically cleaning the titanium sheet with acetone and ultrasonically cleaning the titanium sheet with isopropanol for 1-5 min; ultrasonically cleaning the substrate for 1-5 min by using methanol; and then chemically polishing the titanium sheet by using the volume ratio of HF, nitric acid and water of 1 to (3-4) to (3-5), and cleaning with deionized water.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: and calcining the titanium dioxide nanotube, namely, anodizing the pretreated titanium sheet by using 0.5-1% of ammonium fluoride as electrolyte, and then calcining the anodized titanium sheet.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: calcining the titanium dioxide nanotube, wherein the calcining is carried out at 400-500 ℃ for 2-5 h to prepare TiO 2 A nanotube.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the pretreated titanium sheet is subjected to anodic oxidation, and the electrolytic voltage is 60V.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the calcination is to prepare TiO for 2.5h at 450 DEG C 2 And (4) nano.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the photocatalytic material is catalytically degraded under visible light.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the AgNO 3 The concentration of the solution was 0.1 mol/L.
The invention has the beneficial effects that: the invention is toCdS and Ag nano-particles with diameter of 20nm are coated on TiO 2 The walls of the nanotubes. TiO 2 2 The nano tube array is sensitized by Ag and CdS nano particles, so that the reaction and the photocurrent of visible light are obviously enhanced, and the photoelectrochemical performance is higher. This study also showed that the TiO coating was applied through two or more semiconductors 2 Nanotube surface, enhanced TiO 2 Nanotube photoelectrochemical properties, which ensures more efficient use of a wider range of visible radiation. Meanwhile, the changes of the morphology, the crystal form and the photocatalytic performance of the Ag-doped nanotube are contrastively analyzed, and the method specifically comprises the following steps: (1) TiO prepared by anodic oxidation 2 The nano tubes are uniformly distributed on the surface of the titanium sheet, have high catalytic efficiency, and can improve the degradation rate of methyl orange from 10% to about 74% after 4 hours. (2) Preparation of TiO 2 The optimal conditions for the nanotubes are: the electrolysis voltage is 60V, the electrolysis time is 3 hours, and the exercise temperature and the exercise time are respectively 450 ℃ and 2.5 hours.
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 description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is an SEM image of a nanotube array prepared according to the present invention.
FIG. 2 is TiO 2 Nanotubes (a), CdS-doped TiO 2 The ultraviolet-visible spectrum of the nanotube (b) and the nanotube array (c) of the present invention.
FIG. 3 shows (a) TiO 2 Nanotube, CdS-doped TiO 2 The instant current reaction of the nanotube and the nanotube array of the present invention. (b) TiO doped with CdS and Ag 2 Nanotube surface charge distribution schematic.
FIG. 4 shows TiO irradiation under visible light 2 Nanotube, CdS-doped TiO 2 PC and PEC plots of RHBs for nanotubes, nanotube arrays of the invention.
FIG. 5 is a graph of degradation rates at 30min, 60min, 90min and 120 min.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
firstly, ultrasonically cleaning a titanium sheet by using acetone; ultrasonically cleaning the isopropanol for 5 min; ultrasonically cleaning with methanol for 5 min; then 11.6g of HF, 56.4g of nitric acid and 50g of water are weighed according to the volume ratio of 1: 4: 5 to the HF, the nitric acid and the water respectively for chemical polishing and deionized water cleaning. 0.5% ammonium fluoride was used as the electrolyte.
Titanium sheets are subjected to anodic oxidation according to a conventional method and calcined at 450 ℃ for 2.5h to prepare TiO 2 A nanotube.
50ml of AgNO with the concentration of 0.02mol/L are prepared respectively 3 Solution and 0.1mol/L of Na 2 S and Cdcl 2 And (3) solution.
Subjecting the TiO to a reaction 2 The nano tube is firstly subjected to AgNO of 0.02mol/L 3 Soaking in the solution for 30min, and then soaking at 0.1mol/LNa 2 S and Cdcl 2 And soaking in the solution for 30min to obtain the co-doped nanotube array.
Immersing in methyl orange solution (solution concentration of 0.01g/L) for half an hour, and irradiating under 200W ultraviolet lamp with height controlled at 40 cm.
Calculating the degradation rate: obtaining TiO by the photocatalytic degradation rate of methyl orange 2 The higher the degradation rate of the nanotube is, the better the photocatalytic effect of the sample is, and the degradation rate is related to the measured absorbance value.
FIG. 1 is an SEM image of a nanotube array prepared according to the present invention. FIG. 2 shows TiO 2 Nanotubes (a), CdS-doped TiO 2 Nanotubes (b), the ultraviolet-visible spectrum of the nanotube array (c) of the present invention. FIG. 2 shows TiO 2 Nanotube sample, TiO with CdS nanoparticles 2 Nanotube sample, TiO with CdS and Ag nanoparticles 2 Ultraviolet absorption spectrum of nanotube sample. Curve a in FIG. 3 shows TiO 2 Nanotubes absorb most of the ultraviolet light with wavelengths shorter than 400 nm. After the CdS nanoparticles are deposited, the absorption edge is largely shifted to the visible region as shown by the absorption spectrum. After further sensitization of Ag nanoparticles, TiO 2 Nanotubes absorb all visible light throughout the solar spectrum, making them promising photosensitive materials for solar applications. Testing of TiO by intermittent visible radiation 2 Transient photocurrent response of the nanotubes. During the cyclic switching, the circuit photocurrent density is instantaneous and reproducible. FIG. 3(a) TiO 2 Nanotube, CdS-doped TiO 2 Nanotubes, the instant current response of the nanotube arrays of the present invention. (b) TiO doped with CdS and Ag 2 Nanotube surface charge distribution schematic.
As shown in a of FIG. 3, TiO due to its poor optical absorption property 2 The nanotube electrode did not show any significant enhancement in photocurrent density, only 0mA/cm 2 。TiO 2 The photocurrent density of the saturated nanotube was 15.2mA/cm 2 Higher photocurrent density means more photoinduced electrons from the TiO 2 The nanotubes are transferred to an external circuit counter electrode. This result indicates higher TiO content 2 The nanotube photocurrent is due to visible light absorption by the Ag nanoparticles and efficient transfer of electrons. FIG. 3 (b) shows TiO 2 Microscopic view of charge carrying transfer of nanotube electrodesThe method is described. The narrower band Ag will be readily activated by low energy visible light and attracted by electron-hole pairs. Most of Ag conducts more efficiently than CdS, and Ag is transferred to CdS and TiO 2 Will be suppressed. The quantum effect of Ag nanoparticles can change the conduction band position. The nanometer size of Ag nanoparticles can cause separation of conduction bands, the position of the conduction band is more negative than that of CdS, and electrons are injected from the light-excited Ag to the CdS conduction band. Photoelectrons are collected from Ag, transferred to CdS nanoparticles through interfaces of heterostructures and then transferred to TiO 2 The nanotube surface. Electrons from TiO by an external electrostatic field 2 Nanotube surface, through TiO 2 Interface with Ti into the external loop. And transferring the light generation hole of the valence band of the CdS nano-particles to the Ag nano-particles, and then obtaining a counter electrode. In this way, photo-induced electron-hole pairs are efficiently separated.
FIG. 4 shows TiO irradiation under visible light 2 Nanotube, CdS-doped TiO 2 PC and PEC plots of RHBs for nanotubes, nanotube arrays of the invention. TiO coated with CdS and Ag nanoparticles under visible light irradiation for 5 hours 2 70.6% of RHB were available for nanotube transfer, and TiO coated with CdS nanoparticles for the same exposure time 2 Nanotube transferred RHB and TiO 2 Only 44.2% and 11.8% were available in the RHB for nanotube transfer. TiO with CdS and Ag nanoparticles 2 The nanotubes have higher visible light photocatalytic activity due to their more efficient acquisition of photo-charges and reduced probability of electron pair coalescence.
To study the catalytic time with TiO 2 The relation of the nanotube photocatalysis performance is that firstly, the nanotube is dipped in AgNO of 0.02mol/L 3 Reducing different illumination reduction time in the solution, wherein the selected time is respectively 30min, 60min, 90min and 120min, the degradation rate is as shown in figure 5, and the nanotube catalytic effect curves under different illumination reduction time have common characteristics according to figure 5: with the increase of the illumination time, the degradation rate of the methyl orange is gradually increased, the degradation speed of the methyl orange is fast in 0 to 3 hours, and the degradation rate of the methyl orange is obviously reduced and is smooth in 3 to 4 hours. It can also be seen from the figure thatThe degradation rate of the methyl orange of the nanotube after reduction for 90min is the fastest, and the degradation rate of the solution after 4 hours is about 90 percent at the highest. The photocatalytic efficiency of the nanotube with the reduction time of 120min, 60min, 30min and 15min is slightly worse than that of the nanotube, namely, the photocatalytic efficiency of the nanotube is respectively 87.5%, 84.8%, 79.2% and 77.5%, so that the nanotube array with the reduction time of 90min has the best catalytic effect.
In conclusion, CdS and Ag nano-particles with the diameter of 20nm are coated on TiO 2 The walls of the nanotubes. TiO 2 2 The nano tube array is sensitized by Ag and CdS nano particles, so that the reaction and the photocurrent of visible light are obviously enhanced, and the photoelectrochemical performance is higher. This study also showed that two or more semiconductors were coated on TiO 2 Nanotube surface, enhanced TiO 2 Nanotube photoelectrochemical properties, which ensures more efficient use of a wider range of visible radiation. Meanwhile, the changes of the morphology, the crystal form and the photocatalytic performance of the Ag-doped nanotube are contrastively analyzed, and the method specifically comprises the following steps: (1) TiO prepared by anodic oxidation 2 The nano tubes are uniformly distributed on the surface of the titanium sheet, have high catalytic efficiency, and can improve the degradation rate of methyl orange from 10% to about 74% after 4 hours. (2) Preparation of TiO 2 The optimal conditions for the nanotubes are: the electrolytic voltage is 60V, the electrolytic time is 3 hours, and the exercise temperature and the exercise time are respectively 450 ℃ and 2.5 hours
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. An application of a nanotube array in preparing a photocatalytic material is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
pretreating a titanium sheet;
calcining the titanium dioxide nanotube;
respectively soaking the titanium dioxide nanotubes in AgNO 3 Solution, Na 2 S and Cdcl 2 Obtaining a photocatalytic material in the solution;
wherein, the AgNO 3 The concentration of the solution is 0.02-0.2 mol/L; the Na is 2 The concentration of S is 0.1-0.2 mol/L, and the Cdcl 2 The concentration of the solution is 0.1-0.2 mol/L.
2. Use of the nanotube array of claim 1 for the preparation of a photocatalytic material, characterized in that: the titanium sheet is pretreated by ultrasonically cleaning the titanium sheet with acetone and ultrasonically cleaning the titanium sheet with isopropanol for 1-5 min; ultrasonically cleaning the substrate for 1-5 min by using methanol; and then chemically polishing the titanium sheet by using the volume ratio of HF, nitric acid and water of 1 to (3-4) to (3-5), and cleaning with deionized water.
3. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: and calcining the titanium dioxide nanotube, namely, anodizing the pretreated titanium sheet by using 0.5-1% of ammonium fluoride as electrolyte, and then calcining the anodized titanium sheet.
4. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: calcining the titanium dioxide nanotube, wherein the calcining is carried out at 400-500 ℃ for 2-5 h to prepare TiO 2 A nanotube.
5. Use of the nanotube array of claim 3 for the preparation of a photocatalytic material, characterized in that: the pretreated titanium sheet is subjected to anodic oxidation, and the electrolytic voltage is 60V.
6. Use of the nanotube array of claim 4 for the preparation of a photocatalytic material, wherein: the calcination is to prepare TiO for 2.5h at 450 DEG C 2 And (4) nano.
7. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: the photocatalytic material is catalytically degraded under visible light.
8. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: the AgNO 3 The concentration of the solution was 0.1 mol/L.
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