CN111068647A - Nano TiO (titanium dioxide)2-SnO2Preparation method of solid solution photocatalytic material - Google Patents
Nano TiO (titanium dioxide)2-SnO2Preparation method of solid solution photocatalytic material Download PDFInfo
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Abstract
The invention relates to nano TiO2‑SnO2A preparation method of a solid solution photocatalytic material is characterized in that an amorphous alloy containing low corrosion potential elements or Ti/Sn atomic ratio of 4: 1-6: 1 is used as a precursor, nitric acid is used as a corrosive agent and an oxidant, and nano TiO is synthesized by dealloying and oxidizing2‑SnO2Solid solution, the concrete steps are as followsThe following: (1) four metal raw materials of Cu, Ti, Sn and low-corrosion potential active elements or three metal raw materials of Cu, Ti and Sn are selected and smelted by a vacuum arc furnace to prepare an alloy ingot; (2) heating an alloy ingot by using a magnetic induction coil of vacuum rotary quenching equipment, and spraying alloy liquid onto the surface of a copper roller rotating at a high speed when the alloy is completely melted to obtain an amorphous strip; (3) and (3) under the constant temperature condition, carrying out dealloying oxidation treatment on the amorphous strip in a nitric acid solution. The method is simple to operate, does not involve the use of a large amount of solution and harsh reaction conditions, the minimum unit particle size of the prepared material is 3.5-6 nm, and the catalytic degradation efficiency of the material on rhodamine B under 500W ultraviolet light reaches more than 99%.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to nano TiO2-SnO2A preparation method of solid solution photocatalytic material.
Background
Wide band gap n-type semiconductor TiO2(Eg3.0 to 3.2eV) and SnO2(Eg3.6eV) not only has high photocatalytic activity and stable chemical property, but also has low price and no pollution, and is considered as a photocatalytic material with great potential, and TiO formed by taking the two as the base2-SnO2The solid solution also has semiconductor synthesis effect and special electronic structure, thereby having more excellent photocatalytic performance. Noteworthy, TiO2And SnO2Very similar in crystal structure characteristics and also very similar in ionic radius and electrical characteristics to each other, which is the case for TiO formation2-SnO2Solid solutions provide advantageous conditions. In general, the finer the structure of the material, the greater its specific surface area, which tends to obtain a higher photocatalytic activity. Thus, TiO with very fine structure2-SnO2Solid solution would be a highly desirable photocatalytic material. TiO 22-SnO2The medium and fine nano-structure is formed by dissolving in TiO2Due to the Sn atoms in the crystal lattice, the purpose of hindering the crystal growth can be achieved by providing a large number of different interfaces.
Conventional TiO2-SnO2The solid solution preparation method is mainly a solid phase method (high temperature sintering method). However, the product obtained by the method has large particles and extremely low activity, and the energy consumption of high-temperature calcination for a long time is also large. Thus, one has begun to replace partially or completely the solid phase process by wet chemical processes. For example, Chinese patent CN106430291B uses a solvothermal-calcination two-step method to prepare TiO2-SnO2A solid solution; for another example, Chinese patent CN102992398 synthesizes TiO by sol-gel-hydrothermal method2-SnO2Solid solution. Although these methods solve the drawbacks of the solid phase method, they also bring new problems. First, these methods involve a large number of solutions and associated chemical reactions, and of each solutionThe concentration, the adding proportion and the sequence are strictly controlled, the preparation process is complicated, and the reaction conditions are harsh. In addition, the highest temperature of the solution reaction can reach 220 ℃, and the solution reaction can be realized only by a high-pressure reaction kettle, so that certain potential safety hazard is caused. To solve the above problems, Wang N, et al (Wang N, et al. appl. surf. Sci.,2018,457:200-207.) prepared TiO by dealloying an amorphous alloy with Ti/Sn atomic ratio of 3:1 as a precursor2-SnO2Solid solution. The preparation process of the method is very simple, only one solution is used, the reaction temperature of the solution is only 70 ℃, and the method can be realized by heating in a water bath. However, TiO2-SnO2The synthesis of the solid solution needs to be realized by adding Sn element into the Cu-Ti amorphous alloy, the Sn element has a strong corrosion delaying effect, the preparation period of a sample can be greatly prolonged from 2 days to 7 days, and TiO is caused2-SnO2The coarsening behavior of the solid solution, in turn, adversely affects the photocatalytic activity of the material.
Disclosure of Invention
The invention aims to provide nano TiO aiming at the defects of the prior art2-SnO2The preparation method of the solid solution photocatalytic material is characterized in that amorphous alloy containing low corrosion potential elements or Ti/Sn atomic ratio of 4: 1-6: 1 is used as a precursor, nitric acid is used as a corrosive agent and an oxidant, and the solid solution photocatalytic material is prepared by dealloying under the condition of water bath. The method is simple to operate, does not involve the use of a large amount of solution and harsh reaction conditions, and can prepare the nano TiO with small size and high activity2-SnO2A solid solution photocatalytic material.
The technical scheme adopted by the invention is that nano TiO2-SnO2The preparation method of the solid solution photocatalytic material comprises the following specific steps:
(1) four metal raw materials of Cu, Ti, Sn and low-corrosion potential active elements or three metal raw materials of Cu, Ti and Sn are selected and smelted by a vacuum arc furnace to prepare an alloy ingot, wherein the atomic ratio of Ti to Sn in the alloy ingot is 4: 1-6: 1;
(2) heating the alloy ingot by using a magnetic induction coil of vacuum rotary quenching equipment, opening a gas pressure valve when the alloy is completely melted, and spraying alloy liquid onto the surface of a copper roller rotating at a high speed to obtain an amorphous strip;
(3) under the constant temperature condition, the amorphous strip is subjected to dealloying oxidation treatment in a nitric acid solution to obtain nano TiO2-SnO2A solid solution photocatalytic material.
Performing dealloying oxidation treatment on the amorphous strip in the step (3), performing centrifugal separation, cleaning and drying the precipitate to obtain pure TiO2-SnO2A solid solution powder.
Further, the low corrosion potential active element is one of Y, Al and In.
Further, the content of impurities in the metal raw material is not more than 0.1 wt%.
Furthermore, the atomic ratio of Ti to Sn in the alloy ingot is 4.5: 1-5.5: 1. The atomic ratio of Ti to Sn in the alloy is not too high or too low, the atomic ratio of Ti to Sn is too low, the corrosion delaying effect of Sn element in the dealloying oxidation process is obvious, the corrosion activity of precursor alloy is sharply reduced, the preparation efficiency is low, and the particle size of the obtained product is large; the atomic ratio of Ti to Sn is too high, the semiconductor synthesis effect of the obtained product is not obvious, and the advantages of the solid solution material in the aspect of photocatalytic performance are difficult to embody. In a preferred embodiment of the present invention, the low corrosion potential active element is Y, the purity of the metal material is 99.99 wt%, and the atomic ratio of Ti to Sn in the alloy is 5: 1.
Preferably, the smelting condition of the step (1) is that the vacuum degree is 5.0 multiplied by 10-3And Pa, after introducing argon, firstly melting zirconium ingots to remove oxygen, then melting metal materials, wherein the single melting time is 45-60 s, and melting is carried out for 5 times. The smelting current is 80-200A, and the purity of argon is 99.9%.
The rotary quenching process of the step (2) is carried out in an argon atmosphere, the heating power is 20-30 kW, and the rotating speed of the copper roller is 25.7-31.1 m/s.
The amorphous strips in the step (3) are cut to 3-4 cm, the molar concentration of the nitric acid solution is 14.4M, and the volume ratio of the addition amount of the amorphous strips to the nitric acid solution is 10 g/L; the reaction temperature was 70 ℃.
Nano TiO prepared by the method2-SnO2The minimum unit particle size of the solid solution is 3.5-6 nm, the 2-hour degradation rate of rhodamine B under 500W ultraviolet light is up to more than 99%, the 2-hour degradation rate of rhodamine B under 100W ultraviolet light is more than 40%, and the 2-hour degradation rate of rhodamine B under 100W ultraviolet light in the preferred embodiment is 58.10%.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the corrosion potential of Cu element is higher (+0.342V vs. SHE (standard hydrogen electrode)), the invention improves the corrosion activity of the whole alloy by adding active elements with lower corrosion potential (Y (-2.372V vs. SHE), Al (-1.662V vs. SHE) and In (-0.338V vs. SHE)) into the amorphous alloy to offset for synthesizing TiO2-SnO2The solid solution adds Sn element in the alloy to bring corrosion retarding effect. The method can shorten the preparation period of the material, and can effectively avoid the coarsening action of particles in the product, thereby realizing the nano TiO with small size2-SnO2And (3) fast synthesis of solid solution.
(2) The traditional Ti-Sn alloy not only has uneven element distribution, but also can form a compact surface protective film in a nitric acid solution, so that the oxidation reaction of the elements can not be continuously carried out. The Cu-Ti-Sn-X (X ═ Y, Al and In) amorphous precursor alloy can utilize active atoms (Y/Al/In) with lower corrosion potential to drive Cu atoms to carry out rapid corrosion dissolution, so that Ti atoms and Sn atoms which are completely uniformly distributed In the alloy are sequentially exposed layer by layer, and the uniform, continuous and rapid oxidation process of Ti and Sn elements is realized.
(3) The method of the invention does not relate to high-end experimental equipment and harsh reaction conditions, and the preparation of the catalyst can be realized by directly immersing the amorphous strip into a nitric acid solution. Nitric acid is used as an etchant to remove active atoms (such as Cu, Y, Al and In atoms) In the amorphous alloy, and is used as an oxidant to oxidize exposed Ti and Sn atoms, and nitric acid is used as the etchant and the oxidant simultaneously, so that the use of a large amount of solution is avoided.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of an amorphous precursor alloy involved in the method of the present invention;
FIG. 2 shows a nano TiO prepared by the present invention2-SnO2An X-ray diffraction (XRD) pattern of the solid solution;
FIG. 3 shows the nano TiO prepared in example 4 of the present invention2-SnO2Surface topography (SEM) photographs of solid solutions and EDS analysis results;
FIG. 4 shows a nano TiO compound prepared in example 1 of the present invention2-SnO2Surface topography (SEM) photographs of solid solutions and EDS analysis results;
FIG. 5 shows a nano TiO compound prepared in example 1 of the present invention2-SnO2A surface high magnification topography (HRSEM) photograph of the solid solution;
FIG. 6 shows a nano TiO compound prepared in example 1 of the present invention2-SnO2Surface high magnification topography (HRTEM) photographs of solid solutions;
FIG. 7 shows nano TiO compounds prepared in examples 1 and 4 of the present invention2-SnO2Degradation curves of the solid solution and the blank control group on rhodamine B under 100W ultraviolet light.
Detailed Description
For ease of understanding, the present invention is further described below with reference to specific examples, which are not intended to be unduly limiting upon the invention.
Example 1
Step 1: selecting Cu, Ti, Sn and Y raw materials with the purity of 99.99 wt%, weighing 60% of Cu, 30% of Ti, 6% of Sn and 4% of Y according to the atomic percentage, then placing the prepared metal raw materials and zirconium ingots for deoxidization in different stations of a vacuum arc furnace, vacuumizing to 5.0 x 10-3Pa, and filling argon with the purity of 99.9 percent into the furnace as a protective atmosphere. During smelting, the current is adjusted in real time according to the melting state of the material, and the range is 100-200A. The zirconium ingot is firstly melted to remove oxygen for 40s, the melting is carried out for 1 time, then the metal material is melted, the single melting time is 60s, the melting is carried out for 5 times, and the Cu is prepared by the method60Ti30Sn6Y4And (4) alloy ingot melting.
Step 2: breaking the alloy ingot obtained in the step 1, taking 5g of the broken alloy ingot and putting the broken alloy ingot into special stoneAnd in the quartz tube, fixing the quartz tube right above a copper roller in vacuum rotary quenching equipment, and heating the alloy ingot by using a magnetic induction coil under the argon protective atmosphere, wherein the heating power is 25 kW. When the alloy is completely melted, the air pressure valve is opened, and the alloy liquid is sprayed onto the surface of the copper roller with the rotating speed of 27.5m/s to form Cu60Ti30Sn6Y4Amorphous strips.
And step 3: cu obtained in step 260Ti30Sn6Y4And cutting the amorphous strip to 3-4 cm, placing the amorphous strip in a beaker, and adding a nitric acid solution with the molar concentration of 14.4M into the beaker, so that the ratio of the mass of the amorphous strip to the volume of the nitric acid solution is 10 g/L. Then placing the beaker containing the amorphous strips and the nitric acid solution into a constant-temperature water bath at 70 ℃ for heat preservation, and keeping the temperature of Cu in the solution with the lapse of time60Ti30Sn6Y4The amorphous ribbon gradually changes to TiO2-SnO2The powder exists in the form of powder.
And 4, step 4: centrifugally separating the powder material prepared in the step 3, respectively cleaning precipitates obtained by separation with deionized water and absolute ethyl alcohol, and placing the precipitates in a vacuum drying oven at the temperature of 50 ℃ for 12 hours to obtain the nano TiO with small size2-SnO2Solid solution photocatalytic powder material.
Cu obtained in example 160Ti30Sn6Y4The amorphous strip has the length of 20-50 cm, the width of 2mm and the thickness of 20-30 mu m, and is completely converted into nano TiO in nitric acid solution for 72 hours2-SnO2The size of the smallest unit nanoparticle of the solid solution is 3.5-5 nm, the degradation rate of rhodamine B dye in 2 hours under 500W ultraviolet light is up to more than 99%, and the degradation rate of rhodamine B in 2 hours under 100W ultraviolet light is 58.10%.
Example 2
Step 1: selecting Cu, Ti, Sn and Al raw materials with the purity of 99.99 wt%, weighing 60 percent of Cu, 30 percent of Ti, 6 percent of Sn and 4 percent of Al according to atomic percentage, then placing the prepared metal raw materials and zirconium ingots for deoxidization in different stations of a vacuum arc furnace, vacuumizing to 5.0 x 10-3Pa, in parallelArgon gas with the purity of 99.9 percent is filled into the furnace as protective atmosphere. During smelting, the current is adjusted in real time according to the melting state of the material, and the range is 100-180A. The zirconium ingot is firstly melted to remove oxygen for 40s, the melting is carried out for 1 time, then the metal material is melted, the single melting time is 55s, the melting is carried out for 5 times, and the Cu is prepared by the method60Ti30Sn6Al4And (4) alloy ingot melting.
Step 2: and (2) smashing the alloy ingot obtained in the step (1), taking 5g of smashed alloy ingot and putting the smashed alloy ingot into a special quartz tube, fixing the quartz tube right above a copper roller in vacuum rotary quenching equipment, and heating the alloy ingot by using a magnetic induction coil under the protection of argon, wherein the heating power is 20 kW. When the alloy is completely melted, the air pressure valve is opened, and the alloy liquid is sprayed onto the surface of the copper roller with the rotation speed of 29.3m/s to form Cu60Ti30Sn6Al4Amorphous strips.
And step 3: cu obtained in step 260Ti30Sn6Al4And cutting the amorphous strip to 3-4 cm, placing the amorphous strip in a beaker, and adding a nitric acid solution with the molar concentration of 14.4M into the beaker, so that the ratio of the mass of the amorphous strip to the volume of the nitric acid solution is 10 g/L. Then placing the beaker containing the amorphous strips and the nitric acid solution into a constant-temperature water bath at 70 ℃ for heat preservation, and keeping the temperature of Cu in the solution with the lapse of time60Ti30Sn6Al4The amorphous ribbon gradually changes to TiO2-SnO2The powder exists in the form of powder.
And 4, step 4: centrifugally separating the powder material prepared in the step 3, respectively cleaning precipitates obtained by separation with deionized water and absolute ethyl alcohol, and placing the precipitates in a vacuum drying oven at the temperature of 50 ℃ for 12 hours to obtain the nano TiO with small size2-SnO2Solid solution photocatalytic powder material.
Cu obtained in example 260Ti30Sn6Al4The amorphous strip has the length of 30-60 cm, the width of 2mm and the thickness of 20-30 mu m, and is completely converted into nano TiO in a nitric acid solution for 84 hours2-SnO2Solid solution.
Example 3
Step 1: selectingWeighing Cu, Ti, Sn and In raw materials with the purity of 99.99 wt% according to the atomic percentage of 60 percent of Cu, 30 percent of Ti, 6 percent of Sn and 4 percent of In, then placing the prepared metal raw materials and zirconium ingots for deoxidizing In different stations of a vacuum arc furnace, vacuumizing to 5.0 multiplied by 10-3Pa, and filling argon with the purity of 99.9 percent into the furnace as a protective atmosphere. During smelting, the current is adjusted in real time according to the melting state of the material, and the range is 80-180A. The zirconium ingot is firstly melted to remove oxygen for 40s, the melting is carried out for 1 time, then the metal material is melted, the single melting time is 50s, the melting is carried out for 5 times, and the Cu is prepared by the method60Ti30Sn6In4And (4) alloy ingot melting.
Step 2: and (2) smashing the alloy ingot obtained in the step (1), taking 5g of smashed alloy ingot and putting the smashed alloy ingot into a special quartz tube, fixing the quartz tube right above a copper roller in vacuum rotary quenching equipment, and heating the alloy ingot by using a magnetic induction coil under the protection of argon, wherein the heating power is 20 kW. When the alloy is completely melted, the air pressure valve is opened, and the alloy liquid is sprayed onto the surface of the copper roller with the rotating speed of 31.1m/s to form Cu60Ti30Sn6In4Amorphous strips.
And step 3: cu obtained in step 260Ti30Sn6In4And cutting the amorphous strip to 3-4 cm, placing the amorphous strip in a beaker, and adding a nitric acid solution with the molar concentration of 14.4M into the beaker, so that the ratio of the mass of the amorphous strip to the volume of the nitric acid solution is 10 g/L. Then placing the beaker containing the amorphous strips and the nitric acid solution into a constant-temperature water bath at 70 ℃ for heat preservation, and keeping the temperature of Cu in the solution with the lapse of time60Ti30Sn6In4The amorphous ribbon gradually changes to TiO2-SnO2The powder exists in the form of powder.
And 4, step 4: centrifugally separating the powder material prepared in the step 3, respectively cleaning precipitates obtained by separation with deionized water and absolute ethyl alcohol, and placing the precipitates in a vacuum drying oven at the temperature of 50 ℃ for 12 hours to obtain the nano TiO with small size2-SnO2Solid solution photocatalytic powder material.
Cu obtained in example 360Ti30Sn6In4The amorphous strip has the length of 10-40 cm, the width of 2mm and the thickness of 20-30 mu m, and is completely converted into nano TiO in nitric acid solution for 96 hours2-SnO2Solid solution.
Example 4
Step 1: selecting Cu, Ti and Sn raw materials with the purity of 99.99 wt%, weighing the raw materials according to the atomic percentage of 64 percent of Cu, 30 percent of Ti and 6 percent of Sn, then placing the prepared metal raw materials and zirconium ingots for deoxidizing in different stations of a vacuum arc furnace, vacuumizing to 5.0 multiplied by 10-3Pa, and filling argon with the purity of 99.9 percent into the furnace as a protective atmosphere. During smelting, the current is adjusted in real time according to the melting state of the material, and the range is 100-180A. The zirconium ingot is firstly melted to remove oxygen for 40s, the melting is carried out for 1 time, then the metal material is melted, the single melting time is 45s, the melting is carried out for 5 times, and the Cu is prepared by the method64Ti30Sn6And (4) alloy ingot melting.
Step 2: and (2) smashing the alloy ingot obtained in the step (1), taking 5g of smashed alloy ingot and putting the smashed alloy ingot into a special quartz tube, fixing the quartz tube right above a copper roller in vacuum rotary quenching equipment, and heating the alloy ingot by using a magnetic induction coil under the protection of argon, wherein the heating power is 30 kW. When the alloy is completely melted, the air pressure valve is opened, and the alloy liquid is sprayed onto the surface of the copper roller with the rotating speed of 25.7m/s to form Cu64Ti30Sn6Amorphous strips.
And step 3: cu obtained in step 264Ti30Sn6And cutting the amorphous strip to 3-4 cm, placing the amorphous strip in a beaker, and adding a nitric acid solution with the molar concentration of 14.4M into the beaker, so that the ratio of the mass of the amorphous strip to the volume of the nitric acid solution is 10 g/L. Then placing the beaker containing the amorphous strips and the nitric acid solution into a constant-temperature water bath at 70 ℃ for heat preservation, and keeping the temperature of Cu in the solution with the lapse of time64Ti30Sn6The amorphous ribbon gradually changes to TiO2-SnO2The powder exists in the form of powder.
And 4, step 4: centrifugally separating the powder material prepared in the step 3, respectively cleaning precipitates obtained by separation with deionized water and absolute ethyl alcohol, and placing the precipitates in a vacuum drying oven at 50 DEG CObtaining the nano TiO with small size after 12 hours2-SnO2Solid solution photocatalytic powder material.
Cu obtained in example 464Ti30Sn6The amorphous strip has the length of 40-90 cm, the width of 2mm and the thickness of 20-30 mu m, and is completely converted into nano TiO in nitric acid solution for 120 hours2-SnO2The size of the minimum unit nanoparticle of the solid solution is 4-6 nm, the degradation rate of rhodamine B dye in 2 hours under 500W ultraviolet light is up to more than 99%, and the degradation rate of rhodamine B in 2 hours under 100W ultraviolet light is 41.20%.
Test examples
FIG. 1 is Cu60Ti30Sn6Y4Example 1 Cu60Ti30Sn6Al4Example 2 Cu60Ti30Sn6In4Example 3 Cu64Ti30Sn6Example 4X-ray diffraction (XRD) pattern of the precursor alloy. As can be seen from the figure, all the alloys show typical diffuse scattering peaks, which indicate the amorphous nature, and the amorphous alloy with completely uniform components and structures can be dealloyed and oxidized to synthesize the nano solid solution material with the same uniformity. FIG. 2 is an X-ray diffraction (XRD) pattern of a product formed by dealloying and oxidizing the amorphous alloy (examples 1-4). As can be seen, each alloy is completely transformed after being subjected to nitric acid dealloying oxidation to form a crystal phase with a consistent structure. The shape and position of X-ray diffraction peak of the new phase are between those of standard spectrum PDF No:21-1276 (rutile TiO)2) And PDF No:41-1445 (cassiterite SnO)2) In between, indicating that the corrosion product is TiO2-SnO2In the form of a solid solution. In addition, the positions of diffraction peaks of new phases formed by dealloying in each example are substantially the same, indicating that TiO synthesized by each example2-SnO2The atomic ratio of Ti to Sn in solid solution is the same because the atomic ratio of Ti to Sn in the amorphous precursor alloy is the same.
FIGS. 3 and 4 are TiO prepared in examples 4 and 1, respectively2-SnO2Surface topography (SEM) photographs of solid solutions and related EDS analysis results. As can be seen from the figure, the nano TiO prepared in example 12-SnO2The particle size of the solid solution is significantly smaller than that of the material obtained in example 4. Generally, the smaller the particle size, the larger the contact area of the catalyst with the outside, and the more active the material. Thus the nano TiO prepared in example 12-SnO2Solid solution is a more potential photocatalytic material. From the EDS analysis results of fig. 3 and 4, the nano TiO synthesized in example 4 and example 12-SnO2The specific composition of the solid solution was approximately the same, and was determined to be Ti0.8Sn0.2O2. Fig. 5 is a partial high magnification view (HRSEM) of fig. 4. As can be seen from fig. 5, the nanoparticles shown in fig. 4 are not the smallest unit and consist of finer secondary nanoparticles, and the formation of fine secondary nanostructures can greatly shorten the distance for the photo-generated electrons and holes to migrate to the surface of the catalyst, thereby achieving effective separation of photo-generated carriers. FIG. 6 shows TiO prepared in example 12-SnO2The surface high magnification morphology (HRTEM) photograph of the solid solution shows clearly that the nanoparticles exist in the form of the smallest units with a size of 3.5-5 nm, which corresponds to the secondary nanoparticle structure shown in FIG. 5.
FIG. 7 shows the nano TiO prepared in examples 1 and 42-SnO2Degradation curves of the solid solution and the blank control group on rhodamine B under ultraviolet light (the test equipment is a YCYN-GHX-DAC type photochemical reaction instrument, the ultraviolet light intensity is 100W, the addition amount of the catalyst is 0.5g/L, and the initial concentration of the rhodamine B is 10 mg/L). The results in the figure show that the nano TiO prepared in example 1 and example 42-SnO2The solid solution has extremely high photocatalytic activity, and the degradation efficiency of the solid solution to rhodamine B is obviously higher than that of a blank control group. Wherein the degradation rate of the sample obtained in example 1 in 2 hours is 58.10%, which is much higher than 41.20% of the sample obtained in example 4.
The raw materials and equipment involved in the above examples are obtained by known means, and the procedures used are within the skill of those in the art. In addition, the detailed process flows mentioned in the above examples are only preferred embodiments of the present invention, but the present invention is not limited to the above process flows, that is, the present invention is not meant to be implemented by relying on the above process flows. It should be understood by those skilled in the art that any modification made to the present invention, such as equivalent substitutions of the components of the precursor alloy and the preparation method thereof, within the technical principle and spirit of the present invention, falls within the protection scope of the present invention.
Claims (10)
1. Nano TiO (titanium dioxide)2-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps:
(1) four metal raw materials of Cu, Ti, Sn and low-corrosion potential active elements or three metal raw materials of Cu, Ti and Sn are selected and smelted by a vacuum arc furnace to prepare an alloy ingot, wherein the atomic ratio of Ti to Sn in the alloy ingot is 4: 1-6: 1;
(2) heating the alloy ingot by using a magnetic induction coil of vacuum rotary quenching equipment, opening a gas pressure valve when the alloy is completely melted, and spraying alloy liquid onto the surface of a copper roller rotating at a high speed to obtain an amorphous strip;
(3) under the constant temperature condition, the amorphous strip is subjected to dealloying oxidation treatment in a nitric acid solution to obtain nano TiO2-SnO2A solid solution photocatalytic material.
2. The nano TiO of claim 12-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: performing dealloying oxidation treatment on the amorphous strip in the step (3), performing centrifugal separation, cleaning and drying the precipitate to obtain pure TiO2-SnO2A solid solution powder.
3. A nano TiO according to claim 1 or 22-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the low corrosion potential active element is one of Y, Al and In.
4. A method as claimed in claim 3Nano TiO 22-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the content of impurities in the metal raw materials is not more than 0.1 wt%, and the atomic ratio of Ti to Sn in the alloy ingot is 4.5: 1-5.5: 1.
5. The nano TiO of claim 42-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the low corrosion potential active element is Y, the purity of the metal raw material is 99.99 wt%, and the atomic ratio of Ti to Sn in the alloy is 5: 1.
6. A nano TiO according to claim 1 or 22-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the smelting condition of the step (1) is that the vacuum degree is 5.0 multiplied by 10-3And Pa, after introducing argon, firstly melting zirconium ingots to remove oxygen, then melting metal materials, wherein the single melting time is 45-60 s, and melting is carried out for 5 times. The smelting current is 80-200A, and the purity of argon is 99.9%.
7. A nano TiO according to claim 1 or 22-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the rotary quenching process of the step (2) is carried out in an argon atmosphere, the heating power is 20-30 kW, and the rotating speed of the copper roller is 25.7-31.1 m/s.
8. A nano TiO according to claim 1 or 22-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the amorphous strips in the step (3) are cut to 3-4 cm, the molar concentration of the nitric acid solution is 14.4M, and the volume ratio of the addition amount of the amorphous strips to the nitric acid solution is 10 g/L; the reaction temperature was 70 ℃.
9. The nano TiO of claim 22-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the nano TiO2-SnO2The minimum unit particle size of the solid solution is 3.5-6 nm.
10. The nano TiO of claim 92-SnO2The preparation method of the solid solution photocatalytic material is characterized by comprising the following steps: the nano TiO2-SnO2The 2-hour degradation rate of the solid solution powder to rhodamine B under 500W ultraviolet light reaches more than 99 percent, and the 2-hour degradation rate of the solid solution powder to rhodamine B under 100W ultraviolet light is more than 40 percent.
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