CN110314677B - TiO2 nano powder with different Sn doping amounts prepared by direct solution oxidation method and application thereof - Google Patents
TiO2 nano powder with different Sn doping amounts prepared by direct solution oxidation method and application thereof Download PDFInfo
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 36
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Abstract
The invention relates to the technical field of nano materials, in particular to a method for preparing Sn-doped TiO by a direct solution oxidation method2Nano powder, aiming at the traditional preparation of Sn doped TiO at high temperature (above 300℃)2The defects of the nano powder are that TiO with different Sn doping amounts is prepared at 50-100 ℃ by using tetrabutyl titanate and stannic chloride pentahydrate as raw materials and glacial acetic acid as a stabilizer by a novel direct solution oxidation method2The average grain diameter of the nano powder is 2nm-6nm, and the forbidden band width is 3.1eV-3.4 eV. 0.5 at% Sn doped TiO2The nano powder has the best crystallinity and the highest photocatalysis performance, and the 0.5at percent of Sn is doped with TiO in the experiment2The nanometer powder enters the towel to remove formaldehyde and pure TiO not doped with Sn2Compared with nano powder, the effect is good, and the TiO is widened2The application range of the nano material in the market provides a theoretical basis for the application of the nano material in the surface modification of substrates (such as glass, plastics, textiles and the like) which do not resist high temperature.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a method for preparing TiO with different Sn doping amounts by a direct solution oxidation method2Nano powder and its application.
Background
TiO2As a cheap and stableThe semiconductor oxide with fixed and non-toxic properties can be widely applied in the field of photocatalysis. However, TiO2The band gap of the semiconductor is large (3.2eV), and only ultraviolet light excitation can be received. But TiO22The photocatalyst meets the problem of the necks of the two bottles in the popularization and application processes, and (1) the utilization rate of visible light is low. This is mainly due to TiO2Wide forbidden band (3.23eV), and long wavelength of visible light (λ)>387nm) cannot excite electrons in the valence band, and the energy of this part of the light is around 96% in the solar spectrum (flare et al, functional materials, 2003, 44: 172); (2) TiO22The photon-generated electron-hole pairs are easily recombined due to low photon efficiency (Tang J W et al, Journal of the American Chemical Society, 2008, 130(42): 13885). Thus increasing TiO content2The photocatalytic performance needs to be controlled by TiO2The forbidden band expands the absorption spectrum to the visible region and reduces the recombination rate of photo-generated electron-hole pairs (flare et al, functional materials, 2003, 44: 172). For TiO22Examples of methods for modification are noble metal deposition (Zolotavin P et al, Chemical Physics Letters, 2008, 457(4-6):342), ion doping (Lazau C et al, Materials Letters, 2011, 65:337), dye sensitization (Amao Y et al, Biosensors and Bioelectronics, 2007, 22:1561), and compound semiconductors (Baytis M R et al, Catalysis Letters, 2010, 134: 162). In which on the one hand TiO is synthesized2Nano material, increasing its specific surface area and surface active site, and on the other hand, by applying it to TiO2The material lattice is doped with metal to adjust TiO2The energy band gap is increased, so that the optical response range is expanded, the photocatalytic activity is improved, and TiO can be solved2The photocatalyst has low catalytic efficiency. Synthesis of TiO2The preparation of the high-efficiency photocatalyst of the nano material by metal doping mainly focuses on the traditional methods such as a coprecipitation method, a sol-gel method, a hydrothermal method and the like. The method has the advantages of complex preparation process, various types of required raw materials and high reaction temperature, and also has higher cost because alkaline or organic reagents such as ammonia water, ethanol and the like, and equipment such as a hydrothermal reaction kettle, a resistance furnace (muffle furnace) and the like are frequently used.
Disclosure of Invention
In order to solve the above problems, the present invention provides a novel direct solution oxidationMethod for preparing TiO with different Sn doping amounts and better crystallization property and photocatalysis property at 50-100 DEG C2The crystallinity, band gap and photocatalytic performance of the nano powder are researched, compared with pure TiO2The photocatalytic activity of the towel is improved, the towel is immersed in the towel to remove formaldehyde, the effect is good, and the TiO is widened2The application range of the nano material in the market provides a foundation for the application of the nano material in the surface modification of substrates (such as glass, plastics, textiles and the like) which are not resistant to high temperature.
The invention realizes the purpose through the following technical scheme: sn-doped TiO2The preparation method of nano powder adopts a novel direct solution oxidation method to prepare, and tin tetrachloride pentahydrate and H are stirred2Slowly dripping the mixed solution of O, glacial acetic acid and tetrabutyl titanate into the constant-temperature 30 ℃ acidic aqueous solution with the pH value of 1.5-2.5, stirring for 1-4h, standing and aging for 24-100h to obtain Sn doped TiO2Performing thermal crystallization treatment on the solution at 50-100 ℃ for 15h to obtain Sn-doped TiO2Nano powder, namely photocatalyst.
The doping amount of Sn is 0.5 to 16 at%, for example: 0.5 at%, 2 at%, 4 at%, 8 at%, 16 at%; the tetrabutyl titanate, the glacial acetic acid and the H2The mass ratio of O is 1: 150: 5; the tin chloride pentahydrate H2The volume ratio of the mixed solution of O, glacial acetic acid and tetrabutyl titanate to the acidic aqueous solution is 3-5: 1.
preferably, the pH of the acidic aqueous solution is 1.5 to 2.5, preferably 2.
Preferably, the acidic aqueous solution is glacial acetic acid aqueous solution.
Preferably, the rotation speed of the stirring is 100-600 r/min.
Preferably, the slow addition is a dropwise addition, such as 5-10 mL/min.
Preferably, the temperature of the thermal crystallization treatment is 75 ℃.
Preferably, tin tetrachloride pentahydrate and H are stirred2Slowly dripping the mixed solution of O, acid and tetrabutyl titanate into the constant-temperature 30 ℃ acidic aqueous solution with the pH value of 2, stirring for 2h, standingAging for 72h to obtain Sn doped TiO2Performing thermal crystallization on the solution at 75 ℃ for 15h to obtain Sn-doped TiO2Nano powder, namely photocatalyst.
The invention also relates to the protection of Sn-doped TiO prepared by the method described above2The average grain diameter of the nano powder is 2nm-6nm, and the forbidden bandwidth is 3.1eV-3.4 eV.
Preferably, when the doping amount of Sn is 0.5 at%, tetrabutyl titanate and H2The mass ratio of O to glacial acetic acid is 1: 150: 5, preparing Sn doped TiO by a novel direct solution oxidation method when the thermal crystallization treatment temperature is 75 DEG C2The nano powder has the average grain diameter of 4.83nm, the forbidden bandwidth of 3.12eV and the best photocatalysis performance and crystallinity.
Preferably, in tetrabutyl titanate, glacial acetic acid and H2The mass ratio of O is 1: 150: sn-doped TiO prepared at 5 and 75 DEG C2The nano powder has loose aggregate, fine crystal grains, higher crystallization degree and better photocatalysis performance.
The invention also relates to the protection of Sn-doped TiO as described above2The application of the nano powder as a photocatalyst in formaldehyde removal.
The method can prepare TiO with different Sn doping amounts and good crystallization performance and photocatalysis performance by a novel direct solution oxidation method at 50-100 DEG C2The nano powder can be used for removing formaldehyde by soaking the nano powder into a towel, has good effect and widens TiO2The application range of the nano material in the market provides a theoretical basis for the application of the nano material in the surface modification of substrates (such as glass, plastics, textiles and the like) which do not resist high temperature.
The invention provides a novel direct solution oxidation method, which has the beneficial effects that: aiming at preparing Sn doped TiO at the traditional high temperature (above 300℃)2Defects of the nano powder, TiO with different Sn doping amounts is prepared at 50-100 ℃ by using tetrabutyl titanate and stannic chloride pentahydrate as raw materials and glacial acetic acid as a stabilizing agent by a novel direct solution oxidation method2The nano powder has an average particle diameter of 2-6nm, a forbidden band width of 3.1-3.4 eV, and has high crystallinity and high dielectric constantPhotocatalytic performance. Adding 0.5 at% of Sn doping amount of TiO21200mL of aqueous solution of nano powder is immersed in a towel at 1m3The mass ratio of the powder to the water is 1:120, and the concentration of the formaldehyde after 3 hours is from 0.36mg/m3Reduced to 0.19mg/m3The effect is good. In comparison, pure TiO not doped with Sn2Soaking the nanometer powder water solution in towel to remove formaldehyde, wherein the concentration of formaldehyde is 0.36mg/m after 3h3Reduced to 0.29mg/m3. The reason is that Sn doping changes TiO2The narrow forbidden band reduces the recombination probability of electron hole pairs, thereby improving the photocatalytic efficiency. The method widens TiO2The application range of the nano material in the market provides a theoretical basis for the application of the nano material in the surface modification of substrates (such as glass, plastics, textiles and the like) which do not resist high temperature.
Drawings
FIG. 1 shows TiO compounds with different Sn doping amounts prepared in comparative examples and examples 1 to 5 by thermal crystallization at 75 deg.C2XRD pattern of the nano powder;
FIG. 2 shows TiO compounds with different Sn doping amounts prepared in comparative examples and examples 1 to 5 by thermal crystallization at 75 deg.C2Forbidden band width diagram of the nanometer powder;
FIG. 3 shows pure TiO without Sn doping prepared by a thermal crystallization treatment at 75 ℃ in a comparative example2SEM image (a) of nanopowder and 0.5 at% Sn-doped TiO prepared in example 1 under thermal crystallization treatment at 75 deg.C2SEM picture of nanopowder (b);
FIG. 4 shows pure TiO prepared by a thermal crystallization process at 75 ℃ without Sn doping of a comparative example2EDX Spectrum (a), line Spectrum (b) of nanopowder and 0.5 at% Sn-doped TiO prepared in example 1 under thermal crystallization treatment at 75 deg.C2EDX spectrum (c), line spectrum (d) of the nanopowder.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The invention adjusts the amount of the stannic chloride pentahydrate (the doping amount of Sn is 0.5-16 a)t%) to prepare TiO2Solution precursor is heat treated at 50-100 deg.c, and the heat treated TiO is further treated2XRD test is carried out on the nano powder to determine the crystal structure, the average grain size is measured according to the Sherrer formula D ═ K lambda/beta cos theta, wherein D is the grain size (nm), K is the shape factor constant, 0.89 is taken, lambda is the X-ray wavelength, 0.154056nm is taken, beta is the half-height width (radian) of a diffraction peak, theta is the diffraction angle (degree) of the X-ray, and the grain size range is 2nm-6nm according to calculation. Respectively taking 0.12g of powder, 15mL of deionized water and 0.05mL of dispersant (acrylic acid dispersant) to perform ball milling for 72h at the ball milling rotation speed of 500r/min to obtain slurry, taking 0.1mL of the slurry to perform a light absorption experiment by using an ultraviolet spectrophotometer, and obtaining a formula alpha hv ═ K (hv-E) according to a formulag)1/2The forbidden band width was measured (Liang D D et al, Journal of Materials Science, Materials in Electronics,30:12619), where α is the absorption coefficient, hv is the photon energy (eV), K is a constant, EgThe forbidden band width (eV) is in a range of 3.1eV-3.4eV, and 0.5 at% of Sn-doped TiO2The nano powder has the minimum forbidden bandwidth of 3.12 eV.
Example 1
Preparation of 0.5 at% Sn doped TiO at 75 deg.C2The method for preparing the nano powder comprises the following steps:
(1) and (3) putting 270mL of deionized water into a beaker, adding 15mL of glacial acetic acid to adjust the pH value of the solution to 2 to obtain an acidic aqueous solution, and putting the beaker on a magnetic stirrer to stir continuously at 30 ℃, wherein the stirring speed is 300 r/min.
(2) And putting 270mL of deionized water into another beaker, adding 0.175g of stannic chloride pentahydrate solid to dissolve the stannic chloride pentahydrate solid in the deionized water, then adding 30mL of glacial acetic acid to dissolve for 15min, and then adding 34mL of tetrabutyl titanate to obtain a mixed solution of stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate. (wherein the mass ratio of tetrabutyl titanate, glacial acetic acid and deionized water is 1: 5: 150)
(3) Dropwise adding the mixed solution of the stannic chloride pentahydrate, the water, the glacial acetic acid and the tetrabutyl titanate obtained in the step (2) into the acidic aqueous solution obtained in the step (1) in a stirring state, stirring for 2h, standing and aging for 72h to obtain 0.5 at% of Sn doped solutionHetero TiO22And (3) solution.
(4) Doping the 0.5 at% Sn-doped TiO obtained in the step (3)2The solution is thermally crystallized for 15 hours at the temperature of 75 ℃ to prepare 0.5at percent Sn doped TiO2The average grain diameter of the nano powder is 4.83nm, and the forbidden bandwidth is 3.12 eV.
Example 2
Preparation of 2 at% Sn-doped TiO at 75 deg.C2The method for preparing the nano powder comprises the following steps:
(1) and (3) putting 270mL of deionized water into a beaker, adding 15mL of glacial acetic acid to adjust the pH value of the solution to 2 to obtain an acidic aqueous solution, and putting the beaker on a magnetic stirrer to stir continuously at 30 ℃, wherein the stirring speed is 300 r/min.
(2) And putting 270mL of deionized water into another beaker, adding 0.7012g of stannic chloride pentahydrate solid to dissolve the stannic chloride pentahydrate solid in the deionized water, then adding 30mL of glacial acetic acid, firstly dissolving for 15min, and then adding 34mL of tetrabutyl titanate to obtain a mixed solution of stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate. (wherein the mass ratio of tetrabutyl titanate, glacial acetic acid and deionized water is 1: 5: 150)
(3) Dropwise adding the mixed solution of the stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate obtained in the step (2) into the acidic aqueous solution obtained in the step (1), stirring for 2h, standing and aging for 72h to obtain 2 at% Sn-doped TiO2And (3) solution.
(4) Doping the 2 at% Sn-doped TiO obtained in the step (3)2The solution is thermally crystallized for 15 hours at the temperature of 75 ℃ to prepare 2at percent Sn doped TiO2The average grain diameter of the nano powder is 4.55nm, and the forbidden band width is 3.18 eV.
Example 3
Preparation of 4 at% Sn-doped TiO at 75 deg.C2The method for preparing the nano powder comprises the following steps:
(1) and (3) putting 270mL of deionized water into a beaker, adding 15mL of glacial acetic acid to adjust the pH value of the solution to 2 to obtain an acidic aqueous solution, and putting the beaker on a magnetic stirrer to stir continuously at the temperature of 30 ℃, wherein the stirring speed is 300 r/min.
(2) Dissolving in another beaker, adding 270mL of deionized water, adding 1.4024g of stannic chloride pentahydrate solid to dissolve in the deionized water, then adding 30mL of glacial acetic acid, firstly dissolving for 15min, and then adding 34mL of tetrabutyl titanate to obtain a mixed solution of stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate. (wherein the mass ratio of tetrabutyl titanate, glacial acetic acid and deionized water is 1: 5: 150)
(3) Dropwise adding the mixed solution of the stannic chloride pentahydrate, the water, the glacial acetic acid and the tetrabutyl titanate obtained in the step (2) into the acidic aqueous solution obtained in the step (1) in a stirring state, stirring for 2h, standing and aging for 72h to obtain 4 at% of Sn-doped TiO2And (3) solution.
(4) Doping the 4 at% Sn obtained in the step (3) with TiO2The solution is thermally crystallized for 15 hours at the temperature of 75 ℃ to prepare 4at percent Sn doped TiO2The average grain diameter of the nano powder is 4.14nm, and the forbidden bandwidth is 3.25 eV.
Example 4
Preparation of 8 at% Sn-doped TiO at 75 deg.C2The method for preparing the nano powder comprises the following steps:
(1) and (3) putting 270mL of deionized water into a beaker, adding 15mL of glacial acetic acid to adjust the pH value of the solution to 2 to obtain an acidic aqueous solution, and putting the beaker on a magnetic stirrer to stir continuously at the temperature of 30 ℃, wherein the stirring speed is 300 r/min.
(2) And dissolving the mixed solution in another beaker, adding 270mL of deionized water, adding 2.8048g of stannic chloride pentahydrate solid to dissolve the stannic chloride pentahydrate solid in the deionized water, then adding 30mL of glacial acetic acid, dissolving for 15min, and then adding 34mL of tetrabutyl titanate to obtain a mixed solution of stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate. (wherein the mass ratio of tetrabutyl titanate, glacial acetic acid and deionized water is 1: 5: 150)
(3) Dropwise adding the mixed solution of the stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate obtained in the step (2) into the acidic aqueous solution obtained in the step (1), stirring for 2h, standing and aging for 72h to obtain 8 at% of Sn-doped TiO2And (3) solution.
(4) Doping the 8 at% Sn-doped TiO obtained in the step (3)2The solution is thermally crystallized for 15 hours at the temperature of 75 ℃ to prepare Sn doped TiO with the concentration of 8at percent2Nano meterThe powder has an average particle diameter of 2.66nm and a forbidden band width of 3.29 eV.
Example 5
Preparation of 16 at% Sn-doped TiO at 75 deg.C2The method for preparing the nano powder comprises the following steps:
(1) and (3) putting 270mL of deionized water into a beaker, adding 15mL of glacial acetic acid to adjust the pH value of the solution to 2 to obtain an acidic aqueous solution, and putting the beaker on a magnetic stirrer to stir continuously at the temperature of 30 ℃, wherein the stirring speed is 300 r/min.
(2) And putting 270mL of deionized water into another beaker, adding 5.6096g of stannic chloride pentahydrate solid to dissolve the stannic chloride pentahydrate solid in the deionized water, then adding 30mL of glacial acetic acid, firstly dissolving for 15min, and then adding 34mL of tetrabutyl titanate to obtain a mixed solution of stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate. (wherein the mass ratio of tetrabutyl titanate, glacial acetic acid and deionized water is 1: 5: 150)
(3) Dropwise adding the mixed solution of the stannic chloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate obtained in the step (2) into the acidic aqueous solution obtained in the step (1), stirring for 2h, standing and aging for 72h to obtain 16 at% Sn-doped TiO2And (3) solution.
(4) Doping the 16 at% Sn-doped TiO obtained in the step (3)2The solution is thermally crystallized for 15 hours at the temperature of 75 ℃ to prepare 16at percent Sn doped TiO2The average grain diameter of the nano powder is 2.4nm, and the forbidden bandwidth is 3.4 eV.
Comparative example
Preparation of pure TiO at 75 deg.C2The method for preparing the nano powder comprises the following steps:
(1) and (3) putting 270mL of deionized water into a beaker, adding 15mL of glacial acetic acid to adjust the pH value of the solution to 2 to obtain an acidic aqueous solution, and putting the beaker on a magnetic stirrer to stir continuously at the temperature of 30 ℃, wherein the stirring speed is 300 r/min.
(2) In another beaker, 270mL of deionized water was placed, and 30mL of glacial acetic acid and 34mL of tetrabutyl titanate were added to obtain a mixed solution of glacial acetic acid, water and tetrabutyl titanate. (wherein the mass ratio of tetrabutyl titanate, glacial acetic acid and deionized water is 1: 5: 150)
(3) Dropwise adding the mixed solution of glacial acetic acid, water and tetrabutyl titanate obtained in the step (2) into the acidic aqueous solution obtained in the step (1), stirring for 2h, standing and aging for 72h to obtain pure TiO2And (3) solution.
(4) Pure TiO obtained in the step (3)2The solution is thermally crystallized for 15 hours at the temperature of 75 ℃ to prepare pure TiO2The average grain diameter of the nano powder is 5.2nm, and the forbidden band width is 3.2 eV.
Example 6
TiO with different Sn doping amounts was prepared in the comparative example and examples 1 to 52Grinding the nano powder into powder, respectively taking 0.12g of the powder, 15mL of deionized water and 0.05mL of dispersant (acrylic acid dispersant), mixing, carrying out ball milling for 72 hours at the ball milling rotation speed of 500r/min, respectively filling the obtained slurry into blue-mouth bottles, and carrying out a photocatalysis experiment. And (3) mixing 10mL of slurry and 10mL of methyl orange with the concentration of 0.03g/L, irradiating for 2h under 30W of ultraviolet light with the wavelength of 365nm, respectively measuring the light absorbance of supernatant after the slurry is centrifuged for 8 minutes by 3000rms before and after the irradiation, and calculating the degradation rate of the methyl orange. The degradation rate is (a-B)/a, wherein a is the absorbance before light irradiation and B is the absorbance before light irradiation. The degradation rates of the comparative example and examples 1-5 were calculated as: 57.66%, 84.53%, 64.56%, 55.48%, 39.3% and 22.38%.
Example 7
Sn doped TiO2Nano powder and pure TiO undoped with Sn2The performance comparison of the nano powder for removing formaldehyde is as follows:
10g of 0.5 at% Sn-doped TiO prepared in example 12Mixing the nano powder with 1200mL of tap water, and mixing the mixture with a block of area of 0.5 multiplied by 0.25m2The towel is immersed for 30 minutes, taken out, dried and placed at 1m3The formaldehyde removing performance is measured in the cabinet body, and the concentration of formaldehyde is from 0.36mg/m under visible light illumination for 3 hours3Reduced to 0.19mg/m3。
10g of pure TiO not doped with Sn of the comparative example2Mixing the nano powder with 1200mL of tap water, and mixing the mixture with a block of area of 0.5 multiplied by 0.25m2The towel is immersed for 30 minutes, taken out, dried and placed at 1m3The formaldehyde removing performance is measured in the cabinet body, and the concentration of the formaldehyde is 0.36mg in visible light for 3 hours/m3Reduced to 0.29mg/m3。
Pure TiO with undoped Sn2Compared with the nano powder, 0.5 at% Sn doped TiO2The nano powder has good formaldehyde removing effect.
FIG. 1 shows different Sn-doped amounts of TiO prepared by thermal crystallization at 75 ℃ in comparative example and examples 1 to 52XRD pattern of nano powder. Comparing FIG. 1 with standard card (PCPDF No.21-1272), the Sn doping amounts are respectively 0 at%, 0.5 at%, 2 at%, 4 at%, and 8 at% of TiO2The nanometer powder has diffraction peaks at 25.37, 37.81, 47.99, 53.95, 62.77 and 75.05, which correspond to anatase TiO2(101), (004), (200), (105), (204) and (215), the doped sample also exhibits an anatase crystal structure, and the Sn doping amount is 0 at%, 0.5 at%, 2 at%, 4 at% of TiO2The nano powder has good crystallinity, no diffraction peak of tin oxide appears, water in gel is evaporated slowly and the polycondensation reaction rate is slowed down under a low-temperature system and a proper amount of Sn doping amount, Sn can better replace Ti, tetrabutyl titanate is hydrolyzed more thoroughly, the time for converting solution into solution is prolonged, the nucleation and growth of nano particles are better, and the prepared Sn doped TiO doped with the Sn2The nano powder has the advantages of complete crystal grain development, high crystallinity and the like. TiO with Sn doping amount of 8 at%2TiO with diffraction peak of nano powder slightly shifted to right and Sn doping amount of 16 at%2The diffraction peak of the nano powder is obviously shifted to the right, the crystallinity is poor, and the doping amount of Sn is TiO with 8at percent2The nanometer powder has a diffraction peak of tin oxide, and the doping amount of Sn is 16 at% of TiO2The nano powder obviously has diffraction peak of tin oxide, which shows that the product has solid solution of tin oxide, and when the doping amount of Sn is too high, a great amount of Sn can substitute Ti to enter TiO2In the crystal, a part of tin oxide compound is formed, so that crystallinity is deteriorated.
FIG. 2 shows different amounts of Sn doped TiO prepared at 75 ℃ in comparative examples and examples 1-52Forbidden band width diagram of the nano powder. The doping amounts of Sn are 0 at%, 0.5 at%, 2 at%, 4 at%, 8 at%, and 16 at% of TiO2Forbidden band width of nano powderTiO with Sn doping amount of 0.5 at% and TiO with 3.2eV, 3.12eV, 3.18eV, 3.25eV, 3.28eV, and 3.4eV, respectively2The nano powder has the smallest forbidden bandwidth and the best crystallinity, and the photocatalysis performance is the best, probably because Sn can better replace Ti under the condition of low-temperature system and small amount of Sn doping, but no tin oxide compound is generated, and 0.5at percent of Sn is doped with TiO2The forbidden bandwidth of the nano powder is compared with that of pure TiO2Small and broadened TiO2The critical absorption edge of the photocatalyst can degrade formaldehyde under visible light, thereby improving the photocatalytic performance. TiO with Sn doping amount of 8 at% and 16 at%2The nano powder is generated by tin oxide compound, so the forbidden band width is larger than that of pure TiO2And also its crystallinity is poor, so that its photocatalytic performance is poor.
FIG. 3 shows pure TiO without Sn doping prepared by thermal crystallization at 75 ℃ in a comparative example2SEM image (a) of nanopowder, and 0.5 at% Sn-doped TiO prepared in example 1 by thermal crystallization at 75 deg.C2SEM image (b) of nanopowder. It can be seen from FIG. 3(a) that TiO is not doped with Sn2The agglomeration of nano particles is obvious, the dispersion performance is poor, the particles are large, and the crystallization degree is not high. It can be seen from FIG. 3(b) that the Sn-doped TiO is produced2The nano particles are loose, the particle size is small and is between 2 and 6nm, the crystal grains grow in any orientation, and the degree of crystallization is high.
FIG. 4 shows pure TiO without Sn doping prepared by a thermal crystallization treatment at 75 ℃ in a comparative example2EDX Spectrum (a), line Spectrum (b) of nanopowder and 0.5 at% Sn-doped TiO prepared in example 1 under thermal crystallization treatment at 75 deg.C2EDX spectrum (c) and line spectrum (d) of the nanopowder. As can be seen from FIGS. 4(a, b), the obtained powder has only two elements of Ti and O and is uniformly distributed, and as can be seen from FIGS. 4(c, d), the obtained powder has three elements of Sn, Ti and O and is uniformly distributed, which indicates that Sn is doped with TiO2In the crystal.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. Sn-doped TiO2The preparation method of the nano powder is characterized in that under the stirring state, the mixed solution of tin tetrachloride pentahydrate, water, glacial acetic acid and tetrabutyl titanate is slowly dripped into an acidic aqueous solution with the pH value of 1.5-2.5 at the temperature of 30 ℃, stirred for 1-4h and kept stand for 24-100h to obtain Sn doped TiO2Performing thermal crystallization treatment on the solution at 50-75 ℃ for 15h to obtain Sn-doped TiO2Nano powder;
the doping amount of Sn is 0.5-16 at%; the mass ratio of tetrabutyl titanate to glacial acetic acid to water is 1: 5: 150; the volume ratio of the mixed solution of the stannic chloride pentahydrate, the water, the glacial acetic acid and the tetrabutyl titanate to the acidic aqueous solution is 3-5: 1;
the acidic aqueous solution is glacial acetic acid aqueous solution.
2. The Sn-doped TiO of claim 12The preparation method of the nano powder is characterized in that the slow dropping is dropwise dropping.
3. The Sn-doped TiO of claim 12The preparation method of the nano powder is characterized in that the stirring rotating speed is 100-600 r/min.
4. Sn-doped TiO prepared by the method of any one of claims 1 to 32And (3) nano powder.
5. The Sn-doped TiO of claim 42The nano powder is characterized in that the Sn is doped with TiO2The average grain diameter of the nano powder is 2nm-6 nm.
6. According toThe Sn-doped TiO of claim 42The nano powder is characterized in that the Sn is doped with TiO2The forbidden band width of the nano powder is 3.1eV-3.4 eV.
7. The Sn-doped TiO of claim 42The nano powder is used as a photocatalyst to be applied to formaldehyde removal.
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