负载型TiO2/SBA-15的制备及其光催化还原CO2性能

doi:10.6023/A12070472

化学学报 ›› 2012, Vol. 70 ›› Issue (23): 2412-2418.DOI: 10.6023/A12070472 上一篇下一篇

研究论文

负载型TiO₂/SBA-15的制备及其光催化还原CO₂性能

王会香^a,b, 姜东^a, 吴东^a, 李德宝^a, 孙予罕^a

a 中国科学院山西煤炭化学研究所煤转化国家重点实验室太原 030001;
b 中国科学院大学北京 100049

投稿日期:2012-07-26 发布日期:2012-11-02
通讯作者: 姜东 E-mail: jdred@sxicc.ac.cn
基金资助:
项目受国家自然科学基金(No. 21003150);山西省自然科学基金(No. 2011011006-2)和煤转化国家重点实验室自主研究项目(No. 2011BWZ011)资助.

Synthesis of Supported TiO₂/SBA-15 Catalysts and Their Performance on Photocatalytic Reduction of CO₂

Wang Huixiang^a,b, Jiang Dong^a, Wu Dong^a, Li Debao^a, Sun Yuhan^a

a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001;
b University of Chinese Academy of Sciences, Beijing 100049

Received:2012-07-26 Published:2012-11-02
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21003150), the Natural Science Foundation of Shanxi Province (No. 2011011006-2) and Independent Research Foundation of the State Key Laboratory of Coal Conversion (No. 2011BWZ011).

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摘要/Abstract

以羧基改性的SBA-15 (COOH/SBA-15)和钛酸四丁酯(TB)为原料, 利用COOH/SBA-15表面上高分散的大量羧基将TB锚定, 通过溶剂热处理得到高分散负载型TiO₂/SBA-15催化剂. 产物经XRD, Raman, FT-IR, TEM, N₂吸脱附和UV-Vis表征, 结果显示: 所制备的TiO₂/SBA-15催化剂为比表面大、结晶度较高的锐钛矿TiO₂, TiO₂均匀分散于SBA-15表面, 此外, COOH/SBA-15有效抑制了TiO₂晶粒的长大. 以光催化还原CO₂为探针反应, 考察了TiO₂/SBA-15催化剂在紫外光照射下的光催化性能. 结果表明: 相比于后处理浸渍法制备的光催化剂, 本文制备的TiO₂/SBA-15催化剂表现出了高的光催化还原CO₂活性, 主要产物为甲醇, 且TiO₂最佳负载量为16.5%, 并对相关反应机理做了探讨.

关键词: 羧基改性SBA-15, TiO₂, 光催化还原CO₂

TiO₂/SBA-15 catalysts, TiO₂nanoparticles well dispersed on SBA-15 supporter, have been successfully obtained through a self-assembly aging, carboxylation and subsequent solvothermal process. Firstly, P123 (PEG-PPG-PEG), KCl, (2-cyanoethyl) triethoxysilane (CETES) and tetraethoxysilane (TEOS) were employed to form cyano-modified SBA-15 (CN/SBA-15) in 2.0 mol/L HCl solution by self-assembly aging method. Secondly, carboxyl-modified SBA-15 (COOH/SBA-15) was got through carboxylation treatment in 48% H₂SO₄solution at 95℃ for 24 h. Finally, highly dispersed TiO₂/SBA-15 catalysts were successfully synthesized via solvothermal method at 220℃ for 12 h using COOH/SBA-15 and tetrabutyl titanate (TB) as raw materials. In order to remove the organic compounds and improve the crystallization of TiO₂, the obtained TiO₂/SBA-15 catalysts then were filtrated, washed by absolute ethanol for three times, dried at 80℃ and calcined at 550℃ for 4 h. Notably, the self-assembly and carboxylation process produced large number of good dispersive carboxyl groups (COOH) on SBA-15, which could effectively anchored TB molecules on SBA-15 to promise the highly dispersion of TiO₂on SBA-15. The obtained TiO₂/SBA-15 catalysts have been characterized by X-ray diffraction (XRD), Raman spectrum, Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), nitrogen adsorption and UV-Visible diffuse reflectance spectroscopy (UV-Vis). Above results indicate that the TiO₂/SBA-15 catalysts exhibit large specific surface area and TiO₂ on SBA-15 supporter is anatase phase, they are both play important roles in photocatalytic application. In the current manuscript, the photocatalytic reduction of CO₂ under UV light irradiation as a prober reaction was used to investigate the photocatalytic performance of TiO₂/SBA-15 catalysts. It was found that the obtained catalysts performed high photocatalytic capacity for CO₂ reduction, especially when the loading amount of TiO₂was around 16.5 wt% [n(COOH)/n(TB)=3], the methanol production got maximum which could reach 80 μmol/g-catalyst after 6 h UV light irradiation. Compared with the catalysts which synthesized through simple impregnation method, our TiO₂/SBA-15 catalysts showed the higher activity in photocatalytic reduction of CO₂, owing to the better dispersion and crystallization.

Key words: carboxyl-modified SBA-15, titanium dioxide, photocatalytic reduction of CO₂

引用此文

王会香, 姜东, 吴东, 李德宝, 孙予罕. 负载型TiO₂/SBA-15的制备及其光催化还原CO₂性能[J]. 化学学报, 2012, 70(23): 2412-2418.

Wang Huixiang, Jiang Dong, Wu Dong, Li Debao, Sun Yuhan. Synthesis of Supported TiO₂/SBA-15 Catalysts and Their Performance on Photocatalytic Reduction of CO₂[J]. Acta Chimica Sinica, 2012, 70(23): 2412-2418.

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负载型TiO₂/SBA-15的制备及其光催化还原CO₂性能

Synthesis of Supported TiO₂/SBA-15 Catalysts and Their Performance on Photocatalytic Reduction of CO₂

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