介质和过渡状态的离子和共价稳定通过固体酸在催化过程中
Prashant Deshlahra1, Robert T Carr, Enrique Iglesia
1Department of Chemical and Biomolecular Engineering, University of California , Berkeley, California 94720, United States.
Journal of the American Chemical Society
|October 22, 2014
概括
脱质能 (DPE) 是一个不完整的催化剂描述器. 新的方法评估共价和离子DPE组件,以预测离子对过渡状态中的质子反应性.
科学领域:
- 催化剂是一种催化剂.
- 材料科学 材料科学 材料科学
- 计算化学计算化学
背景情况:
- 反应性描述器通过评估过渡状态和中间稳定性来预测催化剂性能.
- 脱能 (DPE) 是催化固体中布伦斯特德酸强度的理论描述符.
- 甲醇脱水周转率显示了DPE在聚氧甲酸盐 (POM) 集群和矿物酸中的局限性.
研究的目的:
- 研究电荷重组和静电相互作用如何影响DPE.
- 了解这些相互作用如何在W和Mo POM集群和矿物酸中恢复.
- 开发用于离子对过渡状态中的质子反应性的预测描述器.
主要方法:
- 甲醇脱水周转率的机械解释.
- 波恩-哈伯热化学循环的分析.
- 密度函数理论 (DFT) 的计算与静电相互作用估计相结合.
主要成果:
- DPE和酸强度是重要的,但不完整的反应性描述符.
- 莫波姆集群表现出比W波姆集群更有效的电荷重组.
- 与POM集群相比,矿物酸的电荷重组表现较弱.
- 在离子解质后的共价性破坏在离子对中没有完全恢复.
结论:
- 预测反应性描述器需要对共价和离子DPE组件进行单独的评估.
- 建立了一个框架来估计静电相互作用和能量成分.
- 这使得在涉及离子对过渡状态的反应中能够预测质子的反应性质.
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