SO2-4/SiO2表面酸性的红外光谱和密度泛函理论研究

催化学报 , 2007, 28(7): 627-634.

SO2-4/SiO2表面酸性的红外光谱和密度泛函理论研究

郭岱石 ^1, , 马紫峰 ^2, , 蒋淇忠 ^3, , 叶伟东 ^4, , 李春波 ^5,

1.上海交通大学化学工程系,上海,200240

2.上海交通大学化学工程系,上海,200240

3.上海交通大学化学工程系,上海,200240

4.浙江医药股份有限公司新昌制药厂,浙江新昌,312500

5.浙江医药股份有限公司新昌制药厂,浙江新昌,312500

基金项目: 教育部跨世纪优秀人才培养计划(2004) 高等学校博士学科点专项科研项目(20060248064) 国家自然科学基金(20476055)

关键词：二氧化硅 , 硫酸根 , 表面酸性 , 吡啶吸附 , 红外光谱 , 密度泛函理论

FT-IR and Density Functional Theory Studies on Surface Acidity of SO2-4/SiO2

对介孔SiO2及硫酸根促进的SiO2样品进行了原位吡啶吸附红外光谱测试,分别建立了硫酸根促进前后的SiO2表面原子簇模型,用密度泛函理论对其吡啶吸附行为进行了计算,分析了SO2-4/SiO2表面酸性产生的机理. 实验和计算结果表明, SO2-4/SiO2表面不存在Lewis酸中心,原位红外谱图中表征Lewis酸性的特征峰对应于氢键吸附吡啶的环振动,这种氢键作用因SiO2表面的硫酸根促进而得到加强. HSO-4螯合结构为SO2-4/SiO2表面Br(φ)nsted酸中心,其酸强度强于表面磺酸基团修饰的介孔SiO2材料SO3H-MSU, 而弱于HZSM-5. SO2-4/SiO2的酸催化活性源于其表面的Br(φ)nsted酸性.

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