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CO为还原剂同时还原SO2和NO的SnO2-TiO2固溶体催化剂 Ⅲ.催化剂的活性位和反应机理
SnO2-TiO2 Solid Solution Catalyst for Simultaneous Reduction of SO2 and NO by CO Ⅲ. Catalyst Active Sites and Reaction Mechanism
【摘要】 采用显微红外光谱、漫反射红外光谱、瞬变应答反应以及催化剂活性测试等实验手段 ,对SnO2 TiO2 催化剂上SO2 +CO ,NO +CO和SO2 +NO +CO (SRSN)反应的机理及活性位进行了综合研究 .结果表明 ,SO2 +CO和NO +CO反应按典型的Redox机理进行 ,催化剂的表面晶格氧 [O]和氧阴离子空穴 [□ ]([O] [□ ])是Redox反应的活性位 .对于SO2 +CO反应 ,其 [O] [□ ]位于SnO2 TiO2 催化剂中邻近Sn离子和邻近Ti离子的位置 ,邻近Ti离子的 [O] [□ ]的活性比邻近Sn离子的[O] [□ ]的活性高 .NO +CO反应主要在邻近Sn离子的 [O] [□ ]中心上进行 .对于SRSN反应 ,其中的SO2 +CO反应的机理及催化剂的活性位与单纯的SO2 +CO反应相同 ,而其中的NO +CO反应按两种机理进行 :一种和单纯的NO +CO反应相同 ,即按一般的Redox机理进行 ,其活性位为邻近Sn离子的 [O] [□ ]中心 ;另一种按SO2 促Redox反应机理进行 ,其活性位为表面活性硫物种 [SO] .
【Abstract】 The reaction mechanism of SO 2+CO, NO+CO and SO 2+NO+CO (simultaneous reduction of SO 2 and NO, SRSN) reactions on the SnO 2-TiO 2 catalyst and catalyst active sites were investigated by microscopic infrared spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, transient response experiments and catalytic reaction test. SO 2+CO and NO+CO reactions are typical redox reactions and both are carried out on the active sites composed of surface crystal oxygen [O] and oxygen anion vacancy [□] ( [O] - [□] ). In the case of the SO 2+CO reaction, the active sites [O] - [□] are near either Ti ions or Sn ions, and the sites near Ti ions are more active than those near Sn ions. For the NO+CO reaction, however, the active sites are mainly near Sn ions. As for the SRSN reaction, SO 2+CO has the same mechanism as the pure SO 2+CO reaction, while NO+CO proceeds along two paths: one is the typical redox reaction with [O] - [□] as the active sites and the other is the SO 2-assisted NO+CO reaction carried out on the active sites which are consisted of surface active sulfur species [SO] *.
【Key words】 tin dioxide; titania; solid solution; carbon monoxide; reduction; sulfur dioxide; nitric oxide; reaction mechanism; active site;
- 【文献出处】 催化学报 ,Chinese Journal of Catalysis , 编辑部邮箱 ,2004年08期
- 【分类号】O643
- 【被引频次】18
- 【下载频次】368