化学学报 ›› 2005, Vol. 63 ›› Issue (19): 1789-1794. 上一篇    下一篇

研究论文

负载金属对WO3-TiO2光催化剂结构与催化性能的影响

梅长松,钟顺和*   

  1. (天津大学化工学院 天津 300072)
  • 投稿日期:2005-02-18 修回日期:2005-06-08 发布日期:2010-12-10
  • 通讯作者: 钟顺和

Effects of Loaded Metal on Structure and Photocatalytic Performance of Photocatalyst for Synthesis of MAA from Propyl-ene with Carbon Dioxide

MEI Chang-Song, ZHONG Shun-He*   

  1. (College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072)
  • Received:2005-02-18 Revised:2005-06-08 Published:2010-12-10
  • Contact: ZHONG Shun-He

用溶胶-凝胶和浸渍-还原相结合的方法制得M/WO3-TiO2 (M=Pd, Cu, Ni, Ag)光催化剂. 利用X射线衍射(XRD)、程序升温还原(TPR)、红外(IR)、程序升温脱附(TPD)、紫外-可见漫反射光谱(UV-Vis-DRS)和光反应器等技术研究了复合半导体负载金属的物相结构、光吸收性能和光催化反应性能. 结果表明: 金属负载在复合半导体上延迟了TiO2由锐钛矿向金红石相转化, 增强W与载体TiO2的相互作用, 使TiO2光吸收限发生蓝移, 对可见光部分的吸收明显增加; 固体材料吸光性能强弱顺序Pd/WO3-TiO2>Cu/WO3-TiO2>Ag/WO3-TiO2>Ni/WO3-TiO2; 金属Pd对CO2吸附能力过强, 卧式吸附态脱附温度高, 光催化效率不高; 金属Cu对CO2吸附能力适中, CO2与C3H6脱附温度较接近, 实现了“光-表面-热”协同作用, 光量子效率最高, 达到19.7%.

关键词: 复合半导体, 光量子效率, 二氧化碳, 丙烯, 甲基丙烯酸

M/WO3-TiO2 (M=Pd, Cu, Ni, Ag) photocatalysts were prepared by sol-gel and impregna-tion-reaction method. The surface structure, photo absorption performance and photo catalytic performance of M/WO3-TiO2 catalysts were characterized by XRD, XPS, TPR, IR, TPD, UV-Vis-DRS and photoreactor techniques. The experiment results showed that the metal supported on coupled semiconductor WO3-TiO2 restrained the transformation from anatase TiO2 to rutile TiO2. The blue shift of photo absorption edge and increase of the photo absorption capacity to visible light were observed clearly after the addition of metal to WO3-TiO2. The photo absorption per-formance was decreased in the order of Pd/WO3-TiO2, Cu/WO3-TiO2, Ag/WO3-TiO2 and Ni/WO3-TiO2. It can be concluded from the analysis results that the adsorption capacity of CO2 on Pd/WO3-TiO2 was much stronger than others. Its desorption temperature of horizontal adsorption state was increased, so its photo quantum efficiency became lower. Photo quantum efficiency of Cu/WO3- TiO2 was the highest, on which desorption temperature of CO2 was approximate to C3H6. Photo quantum efficiency of the reaction reached 19.7% and the se-lectivity to MAA was over 95% on Cu/WO3-TiO2 catalyst under proper reaction conditions: vs (space velocity) 200 h-1, pressure 0.1 MPa, temperature 110 ℃ and UV light inten-sity 0.65 mW•cm-2. Loaded metallic Cu on coupled semiconductor WO3-TiO2 realized photo- surface-thermal synergistic effects and improved photo quantum efficiency.

Key words: coupled semiconductor, photo quantum efficiency, carbon dioxide, propylene, methacrylic acid