密度泛函理论研究分子筛相邻双酸性位对乙烯质子化反应的影响

催化学报 , 2011, 32(6): 1056-1062. doi: 10.3724/SP.J.1088.2011.10110

密度泛函理论研究分子筛相邻双酸性位对乙烯质子化反应的影响

任珏 ^1, , 周丹红 ^2, , 李惊鸿 ^3, , 曹亮 ^4, , 邢双英 ^5,

1.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

2.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

3.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

4.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

5.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

基金项目: 国家自然科学基金(20073058)

关键词： HZSM-5分子筛 , 乙烯质子化 , Br(o)nsted-酸性位 , 相邻酸性位 , 密度泛函理论

Density Functional Theory Study of Ethylene Protonation over HZSM-5 Zeolite with Neighboring Br(o)nsted Acid Sites

采用密度泛函理论B3LYP/6-31G(d,p)方法,研究了HZSM-5分子筛上不同酸性位以及相邻双酸性位对乙烯质子化反应的影响,考察了乙烯吸附、质子化反应过渡态和表面乙氧中间体的几何结构、原子电荷和相关能量.结果表明,存在紧邻酸性位的分子筛酸性明显减弱,乙烯分子的吸附能降低,但质子转移过渡态的活化能仅略有降低;次邻酸性位对酸性强度的影响很小,对乙烯质子化的影响也可忽略.乙烯质子化反应的活化能及表面乙氧中间体的生成能与酸强度没有必然关系,但与酸性位落位及周围的化学环境和空间环境有关.过渡态结构越接近碳正离子,活化能越高.

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密度泛函理论研究分子筛相邻双酸性位对乙烯质子化反应的影响

Density Functional Theory Study of Ethylene Protonation over HZSM-5 Zeolite with Neighboring Br(o)nsted Acid Sites

参考文献