Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal-Organic Framework for Ethylene Dimerization
Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal-Organic Framework for Ethylene Dimerization
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DOI：
10.1021/acs.jpcc.6b07362
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发表时间：
2016-10-20
影响因子：
3.7
通讯作者：
Gagliardi, Laura
中科院分区：
文献类型：
--
作者：
Bernales, Varinia;League, Aaron B.;Gagliardi, Laura
本文通过量子化学方法表征负载在金属有机骨架（MOF）NU-1000的氧化锆样节点上的钴（II）单位点催化剂的催化性能，并与掺入镍（II）作为活性过渡金属的同构类似物进行比较。原子层沉积在MOFs和催化的机制，研究使用密度泛函理论。我们比较了钴和镍的催化活性安装在氧化锆样的节点乙烯二聚，考虑三个合理的途径。采用多组态波函数理论方法进一步研究了关键过渡态和中间体的电子结构。最后，我们报告确认的Co催化活性乙烯二聚的实验所提示的计算预测。
The catalytic performance of a cobalt(II) single site catalyst supported on the zirconia-like nodes of the metal organic-framework (MOF) NU-1000 is herein characterized by quantum chemical methods and compared to an iso-structural analogue incorporating nickel(II) as the active transition metal. The mechanisms of atomic layer deposition in MOFs and of catalysis are examined using density functional theory. We compare the catalytic activity of Co and Ni installed on the zirconia-like nodes for ethylene dimerization, considering three plausible pathways. Multiconfigurational wave function theory methods are employed to further characterize the electronic structures of key transition states and intermediates. Finally, we report confirmation of Co catalytic activity for ethylene dimerization from experiments that were prompted by the computational prediction.