3D多级孔rGO/TiO2复合材料的构筑及其光催化性能研究

doi:10.15541/jim20200682

摘要/Abstract

摘要：

研究以聚苯乙烯(PS)微球为模板、氧化石墨烯(GO)和钛酸四丁酯(TBT)为原料, 采用溶胶-凝胶法, 利用GO与PS上的官能团和TiO₂前驱体的多重配位反应, 制备了3D多级孔rGO/TiO₂(PS)复合材料。通过不同手段对样品的结构和形貌进行表征, 研究了PS添加量对rGO/TiO₂复合材料晶体结构、微观形貌及光催化性能的影响。分别在模拟紫外光和可见光下, 以盐酸四环素(TTCH)为目标污染物对不同PS加入量制备的3D多级孔rGO/TiO₂(PS)复合材料的光催化性能进行评价, 并在模拟可见光下, 对3D多级孔rGO/TiO₂(5wt%PS)复合材料进行了多次循环回收测试。结果表明: rGO/TiO₂(PS)复合材料具有3D多级孔块体结构, GO作为基体的增强相通过Ti-O-C键保持多级孔刚性骨架结构的稳定。引入PS增大了rGO/TiO₂(PS)复合材料的比表面积, 3D多级孔rGO/TiO₂(7wt% PS)复合材料对TTCH吸附效率最高, 而3D多级孔rGO/TiO₂(5wt%PS)复合材料光催化活性和稳定性最高, 且经过4次循环回收测试, 其光催化效率仍达81.02%; 模板剂PS的最佳引入量为5wt%。

关键词: PS模板, rGO/TiO₂, 3D多级孔, 紫外光, 可见光

Abstract:

Utilizing polystyrene (PS) microspheres as templates, and graphene oxide (GO) and tetrabutyl titanate (TBT) as raw materials, 3D hierarchical pore rGO/TiO₂(PS) composites were fabricated by Sol-Gel method based on multiple coordination reactions. The structure and morphology of 3D hierarchical pore rGO/TiO₂(PS) composites were characterized, and the effects of PS addition on crystal structure, microscopic morphology and photocatalytic performance of rGO/TiO₂ composites were studied. Under simulate ultraviolet light and visible light irradiation, tetracycline hydrochloride (TTCH) using as the target pollutant, the photocatalytic performance of 3D hierarchical pore rGO/TiO₂(PS) composites prepared with different PS addition was evaluated. Under simulated visible light irradiation, the 3D hierarchical pore rGO/TiO₂(5wt%PS) composites were subjected to multiple recycling tests. The results show that the rGO/TiO₂(PS) composites have a 3D hierarchical pore bulk structure. As the reinforcing phase of matrix, GO keeps stability of multistage pore rigid skeleton structure through Ti-O-C bond. Furthermore, the introduction of PS increases the specific surface area of the rGO/TiO₂(PS) composites. The 3D hierarchical pore rGO/TiO₂(7wt%PS) composite has the highest adsorption efficiency for TTCH, while the 3D hierarchical pore rGO/TiO₂(5wt%PS) composite has the highest photocatalytic activity and stability, which photocatalytic efficiency still reaches 81.02% after 4 cycles of recycling tests; the best addition amount of template PS is 5wt%.

Key words: PS template, rGO/TiO₂, 3D multistage aperture, ultraviolet light, visible light

中图分类号:

TQ174

李翠霞, 孙会珍, 金海泽, 史晓, 李文生, 孔文慧. 3D多级孔rGO/TiO₂复合材料的构筑及其光催化性能研究[J]. 无机材料学报, 2021, 36(10): 1039-1046.

Li Cuixia, SUN Huizhen, JIN Haize, SHI Xiao, LI Wensheng, KONG Wenhui. Construction and Photocatalytic Performance of 3D Hierarchical Pore rGO/TiO₂ Composites[J]. Journal of Inorganic Materials, 2021, 36(10): 1039-1046.

图/表 9

图1 TiO2及不同PS添加量rGO/TiO2(PS)的XRD图谱

Fig. 1 XRD patterns of TiO2 and rGO/TiO2(PS) prepared with different PS additions

图2 PS(a)和rGO/TiO2(b)的TEM照片, rGO/TiO2(5wt%PS)复合材料的SEM照片(c)(插图为对应TEM照片)及rGO/TiO2 (5wt%PS)的O, C和Ti的HADDF图像和EDS面分布(d)

Fig. 2 TEM images of PS(a) and rGO/TiO2(b), SEM image (c) of rGO/TiO2 (5wt%PS) composite (inset displaying TEM image) and HADDF image and EDS mappings of O, C and Ti in rGO/TiO2 (5wt%PS)(d)

图3 3D多级孔rGO/TiO2光催化剂的形成机理

Fig. 3 Formation mechanism of rGO/TiO2 photocatalyst with 3D hierarchical pore

图4 rGO/TiO2和rGO/TiO2(5wt%PS)的氮气吸附-脱附等温线(a)和孔径分布曲线(b)

Fig. 4 Nitrogen adsorption-desorption isotherms (a) and pore diameter distribution curves (b) of rGO/TiO2 and rGO/TiO2 (5wt%PS)

图5 TiO2、rGO/TiO2和rGO/TiO2(5wt%PS)的紫外-可见漫反射光谱(a)及其禁带宽度(b); TiO2和不同PS加入量制备的rGO/TiO2(PS)复合材料的荧光发射光谱(c)

Fig. 5 UV-visible diffuse reflection spectra (a) and band gap width (b) of TiO2, rGO/TiO2 and rGO/TiO2(5wt%PS); fluorescence emission spectra of TiO2 and rGO/TiO2(PS) prepared with different PS additions (c) Colorful images are available on website

图6 rGO/TiO2(5wt%PS)样品的XPS能谱分析

Fig. 6 X-ray photoelectron spectra of rGO/TiO2(5wt%PS) (a) full spectrum; (b) O1s; (c) C1s; (d) Ti2p Colorful images are available on website

图7 TiO2及不同PS加入量制备的rGO/TiO2(PS)复合材料的吸附率(a), 可见光(b)和紫外光(c)下的光催化效率

Fig. 7 Adsorption rate (a), photocatalytic efficiency under visible light (b) and ultraviolet light (c) of TiO2 and rGO/TiO2(PS) prepared with different PS additions Colorful images are available on website

图8 rGO/TiO2(5wt%PS)样品回收循环测试(a), rGO/TiO2和rGO/TiO2(5wt%PS)的光催化反应动力学拟合分析(b)

Fig. 8 Recycling test of rGO/TiO2(5wt%PS) sample (a), and Kinetic fitting analysis of photocatalytic reaction of rGO/TiO2 and rGO/TiO2(5wt%PS) (b)

图9 多级孔rGO/TiO2(PS)复合材料光催化降解盐酸四环素的机理图

Fig. 9 Mechanism diagram of photocatalytic degradation of tetracycline hydrochloride by hierarchical pore rGO/TiO2(PS) composite material

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3D多级孔rGO/TiO₂复合材料的构筑及其光催化性能研究

Construction and Photocatalytic Performance of 3D Hierarchical Pore rGO/TiO₂ Composites

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