Wu Zhongbiao, Sheng Zhongyi, Wang Haiqiang, Liu Yue
Department of Environmental Engineering, Zhejiang University, Hangzhou, PR China.
Chemosphere. 2009 Sep;77(2):264-8. doi: 10.1016/j.chemosphere.2009.07.060. Epub 2009 Aug 19.
This study has been undertaken to investigate the relationship between Pd oxidation states on TiO(2) photocatalysts and their photocatalytic oxidation behaviors of NO. Three types of Pd-modified TiO(2) with different Pd oxidation states were prepared by wet impregnation method, neutralization method and photodeposition method, respectively. And these Pd-modified photocatalysts were characterized by X-ray diffraction analysis, X-ray photoelectron spectrum analysis (XPS), UV-Vis diffuse reflectance spectra and temperature programmed desorption (TPD). It was found from XPS results that the dominant oxidation states of Pd on these Pd-modified TiO(2) catalysts were Pd(2+), PdO, and Pd(0), respectively. NO-TPD results showed that the NO adsorption capacity was improved greatly by the modification of Pd(2+) ions. The activity tests showed that Pd-modified TiO(2) by a wet impregnation method increased photocatalytic activity compared to pure TiO(2) (Degussa P25). It was concluded that Pd(2+) ions on as-prepared TiO(2) catalysts provided key contributions to the improvement of photocatalytic activity. However, Pd(0) and PdO deposits on TiO(2) almost had no positive effect on NO oxidation. The mechanism of photocatalytic oxidation of NO in gas phase over Pd-modified TiO(2) was also proposed.
本研究旨在探究二氧化钛(TiO₂)光催化剂上钯(Pd)的氧化态与其对一氧化氮(NO)的光催化氧化行为之间的关系。分别采用湿浸渍法、中和法和光沉积法制备了三种具有不同钯氧化态的钯改性TiO₂。并通过X射线衍射分析、X射线光电子能谱分析(XPS)、紫外可见漫反射光谱和程序升温脱附(TPD)对这些钯改性光催化剂进行了表征。XPS结果表明,这些钯改性TiO₂催化剂上钯的主要氧化态分别为Pd²⁺、PdO和Pd⁰。NO-TPD结果表明,Pd²⁺离子的改性极大地提高了NO的吸附能力。活性测试表明,与纯TiO₂(德固赛P25)相比,湿浸渍法制备的钯改性TiO₂提高了光催化活性。得出的结论是,所制备的TiO₂催化剂上的Pd²⁺离子对光催化活性的提高起到了关键作用。然而,TiO₂上的Pd⁰和PdO沉积物对NO氧化几乎没有积极影响。还提出了气相中Pd改性TiO₂上NO光催化氧化的机理。