B,N-SnO2/TiO2光催化剂的制备及其光催化性能研究

doi:10.6023/A21050242

摘要/Abstract

为了提高TiO₂在可见光下的光催化活性, 采用聚合物前驱体法制备了B,N共掺杂的SnO₂/TiO₂(B,N-SnO₂/TiO₂)粉体型光催化剂. 进一步为了提高光催化剂的实用性, 通过浸渍-裂解法制备了氧化铝纤维毡负载的B,N-SnO₂/TiO₂光催化剂. 利用X射线衍射仪、场发射扫描电子显微镜、场发射透射电子显微镜、X射线光电子能谱、比表面积分析仪、紫外-可见分光光度计等对其进行了表征. 以氧氟沙星水溶液为模拟污染物, 考察了B,N-SnO₂/TiO₂粉体型光催化剂和负载型光催化剂的可见光催化活性及稳定性. 结果表明, 该粉体型光催化剂在可见光下光照15 min, 对氧氟沙星的降解率可达98.3%. 负载型光催化剂也表现出了良好的光催化性能及可重复性和稳定性, 在21次重复使用后光催化性能几乎不发生变化.

关键词: 二氧化钛, 二氧化锡, 氧氟沙星, 负载, 可见光催化降解

In order to improve the photocatalytic activity of TiO₂ under visible light, B,N-codoped SnO₂/TiO₂ (B,N-SnO₂/TiO₂) powder photocatalysts were prepared by polymer precursor method, and to further improve the practicability of B,N-SnO₂/TiO₂ photocatalyst, alumina fabrics immobilized B,N-SnO₂/TiO₂ catalyst was prepared by precursor impregnation and pyrolysis method. The typical experimental procedure for synthesis of B,N-SnO₂/TiO₂ powder photocatalysts is as follows: First, tetrapropylorthotitanate (TNPT) was mixed with PEG-600 and Sn(OPr)₄ under magnetic stirring and refluxed for 2 h. Then boric acid was added. Acetamide and acetylacetone were added to the system after boric acid was dissolved completely. Finally, a mixture of deionized water and n-propanol were added dropwise. The whole solution were reflux for 1 h and then the B,N-SnO₂/TiO₂ precursor was obtained by rotary evaporation method. The precursor was placed in a quartz tube furnace and calcined at a heating rate of 3 ℃/min to 450 ℃ for 30 min to obtain B,N-SnO₂/TiO₂ powder type photocatalyst. Supported photocatalysts was prepared as follows: The precursor solution of B,N-SnO₂/TiO₂ was diluted with n-propanol and heated at 100 ℃ for 1 h. The alumina fabrics was immersed in the loaded solution and heated at 100 ℃ for 1 h. Then the precursor immersed fabrics was dried by rotary evaporation method. Supported photocatalysts were obtained by calcining the dried fabrics at 450 ℃ for 30 min in air atmosphere. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and UV-Vis diffuse reflectance spectra (UV-DRS). B,N-SnO₂/TiO₂ powder photocatalysts were predominantly homogeneous anatase phase. The introduction of boron inhibited the growth of anatase phase crystal, and the grain size was 15 nm, showing a stacking structure. The results of HRTEM and energy dispersive spectrometer (EDS) showed that SnO₂ and TiO₂ constructed heterostructure, and the doped elements existed and distributed evenly. Boron and nitrogen co-doping and heterojunction structure effectively improved the separation ability of photogenerated carriers. The photocatalytic activities of B,N-SnO₂/TiO₂ powder photocatalysts were investigated using ofloxacin solution as simulated pollutant. The results indicated that the degradation ratio of ofloxacin reached 98.3% in 15 min under visible light. The B,N-SnO₂/TiO₂-loaded Al₂O₃ fabrics also showed excellent photocatalytic performance, with a thickness of about 100 nm powder photocatalysts on the surface of Al₂O₃ fabrics, and the heterostructure still existed. The results showed that the degradation rate of ofloxacin was 68.7% under visible light irradiation for 120 min, and the photocatalytic performance was almost unchanged after repeated use for 21 times.

Key words: TiO₂, SnO₂, ofloxacin, loaded, visible light catalytic degradation

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马智烨, 叶丽, 吴雨桓, 赵彤. B,N-SnO₂/TiO₂光催化剂的制备及其光催化性能研究[J]. 化学学报, 2021, 79(9): 1173-1179.

Zhiye Ma, Li Ye, Yuhuan Wu, Tong Zhao. Preparation and Photocatalytic Performance of B,N-SnO₂/TiO₂ Photocatalyst[J]. Acta Chimica Sinica, 2021, 79(9): 1173-1179.

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图/表 15

图1. B,N-SnO2/TiO2和纯TiO2的XRD图

Figure 1. XRD patterns of B,N-SnO2/TiO2 and pure TiO2

样品	Titanium	Tin	Nitrogen	Boron
B,N-SnO₂/TiO₂	53.1	2.6	<1	1.0

表1. B,N-SnO2/TiO2的化学成分组成(质量分数/%)

Table 1. Chemical composition of B,N-SnO2/TiO2 (weight fraction/%)

图2. B,N-SnO2/TiO2的B, N, O, Ti和Sn的XPS图像

Figure 2. XPS images of B, N, O, Ti and Sn of B,N-SnO2/TiO2

图3. B,N-SnO2/TiO2的(A) SEM图像; (B, C) TEM图像; (D) SAED图像

Figure 3. (A) SEM image; (B, C) TEM images; (D) SAED image of B,N-SnO2/TiO2

图4. B,N-SnO2/TiO2粉体型光催化剂的X射线能量色散光谱图

Figure 4. EDS images of B,N-SnO2/TiO2

图5. B,N-SnO2/TiO2和纯TiO2的UV-Vis DRS图

Figure 5. UV-Vis DRS images of B,N-SnO2/TiO2 and pure TiO2

图6. B,N-SnO2/TiO2和纯TiO2的(αhν)0.5-hν图

Figure 6. Plots of (αhν)0.5-hν for B,N-SnO2/TiO2 and pure TiO2

图7. B,N-SnO2/TiO2和纯TiO2的光致发光谱图

Figure 7. PL spectrum for sample B,N-SnO2/TiO2 and pure TiO2

图8. 负载型光催化剂的SEM图和各元素EDS面扫结果图

Figure 8. SEM image and EDS mapping images of each element of supported photocatalyst

图9. 负载型光催化剂的TEM图

Figure 9. TEM images of supported photocatalyst

图10. 负载型光催化剂的稳定性测试

Figure 10. Cycling tests of photodegradation of ofloxain of supported photocatalyst

图11. 负载型光催化剂的循环利用重量图

Figure 11. Mass of supported photocatalyst after each cycle of photodegradation test

图12. 负载型光催化剂在(A)光催化前和(B)光催化后的SEM图

Figure 12. SEM images of supported photocatalysts (A) before and (B) after photocatalysis

图13. 可见光下不同捕获剂对B,N-SnO2/TiO2降解活性的影响结果图

Figure 13. Photodegradation efficiencies of ofloxacin by B,N-SnO2/ TiO2 with different trapping agents added under visible light

图14. B,N-SnO2/TiO2光催化机理简要示意图

Figure 14. Schematic illustration of photocatalysis process of B,N-SnO2/TiO2

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B,N-SnO₂/TiO₂光催化剂的制备及其光催化性能研究

Preparation and Photocatalytic Performance of B,N-SnO₂/TiO₂ Photocatalyst

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