Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4l,Journal of the American Chemical Society

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Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4l
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-01-04 , DOI: 10.1021/jacs.6b10300
Eric D. Metzger ₁ , Robert J. Comito ₁ , Christopher H. Hendon ₁ , Mircea Dincă ₁

Affiliation

A recently developed metal-organic framework (MOF) catalyst for the dimerization of ethylene has a combination of selectivity and activity that surpasses that of commercial homogeneous catalysts, which have dominated this important industrial process for nearly 50 years. The uniform catalytic sites available in MOFs provide a unique opportunity to directly study reaction mechanisms in heterogeneous catalysts, a problem typically intractable due to the multiplicity of coordination environments found in many solid catalysts. In this work, we use a combination of isotopic labeling studies, mechanistic probes, and DFT calculations to demonstrate that Ni-MFU-4l operates via the Cossee-Arlman mechanism, which has also been implicated in homogeneous late transition metal catalysts. These studies demonstrate that metal nodes in MOFs mimic homogeneous catalysts not just functionally, but also mechanistically. They provide a blueprint for the development of advanced heterogeneous catalysts with similar degrees of tunability to their homogeneous counterparts.

中文翻译：

Ni-MFU-4l中单位点类分子催化乙烯二聚反应机理

最近开发的一种用于乙烯二聚的金属有机骨架 (MOF) 催化剂的选择性和活性组合超过了商业均相催化剂，后者主导了这一重要的工业过程近 50 年。MOF 中可用的均匀催化位点为直接研究多相催化剂中的反应机制提供了独特的机会，由于许多固体催化剂中存在多种配位环境，这个问题通常难以解决。在这项工作中，我们结合使用同位素标记研究、机械探针和 DFT 计算来证明 Ni-MFU-4l 通过 Cossee-Arlman 机制运行，这也与均相后过渡金属催化剂有关。这些研究表明，MOF 中的金属节点不仅在功能上而且在机械上都模拟了均相催化剂。它们为开发具有与其均相催化剂相似程度的可调性的先进多相催化剂提供了蓝图。

更新日期：2017-01-04

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