The catalytic activity and adsorption in faujasite and ZSM-5 zeolites: the role of differential stabilization and charge delocalization
The catalytic activity and adsorption in faujasite and ZSM-5 zeolites: the role of differential stabilization and charge delocalization
复制标题
八面沸石和 ZSM-5 沸石的催化活性和吸附：差异稳定和电荷离域的作用
DOI：
10.1039/d1cp05851g
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发表时间：
2022
影响因子：
3.3
通讯作者：
Fedorov Dmitri G.
中科院分区：
文献类型：
--
作者：
Nakamura Taiji;Fedorov Dmitri G.
采用量子力学碎片分子轨道方法结合周期性边界条件研究了工业上重要的 ZSM-5 和八面沸石催化剂上发生的吸附和化学反应。设计并测试了合适的碎片模式，提供了使用碎片方法计算真实材料的重要案例研究。与完整的计算相比，证明了良好的准确性，并且与可用的实验数据获得了良好的一致性。绘制了八面沸石上对二甲苯的完整生产周期。通过分配分析分析，沸石在脱水反应中的催化作用归因于沸石上负电荷的离域。另一方面，沸石在第尔斯-阿尔德反应中势垒的增加归因于反应物相对于过渡态的优先稳定，如客体-沸石相互作用能所证明的。
Adsorption and chemical reactions occurring on industrially important ZSM-5 and faujasite zeolite catalysts are investigated with the quantum-mechanical fragment molecular orbital method combined with periodic boundary conditions. Suitable fragmentation patterns are devised and tested providing important case studies of computing real materials with fragmentation methods. A good accuracy is demonstrated in comparison to full calculations, and a good agreement with the available experimental data is obtained. The full production cycle of p-xylene on faujasite zeolite is mapped. The catalytic role of the zeolite in the dehydration reaction, analyzed with the partition analysis, is attributed to the delocalization of the negative charge over the zeolite. On the other hand, an increase of the barrier in the Diels–Alder reaction by the zeolite is attributed to the preferential stabilization of the reactants over the transition state as demonstrated by the guest-zeolite interaction energy.