Hammett Parameter in Microporous Solids as Macroligands for Heterogenized Photocatalysts
Hammett Parameter in Microporous Solids as Macroligands for Heterogenized Photocatalysts
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DOI：
10.1021/acscatal.7b03998
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发表时间：
2018-01
期刊：
影响因子：
12.9
通讯作者：
F. Wisser;Pierrick Berruyer;Luis Cardenas;Yorck Mohr;E. A. Quadrelli;A. Lesage;D. Farrusseng;J. Canivet
中科院分区：
文献类型：
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作者：
F. Wisser;Pierrick Berruyer;Luis Cardenas;Yorck Mohr;E. A. Quadrelli;A. Lesage;D. Farrusseng;J. Canivet
在这里，我们提出了一系列的多相催化剂的基础上的金属有机框架和微孔聚合物作为大配体的多相有机金属配合物。我们发现，均相和多相催化剂遵循相同的线性相关性之间的电子效应的配体，描述的Hammett参数，和催化活性。这种相关性突出了活性催化中心周围的局部电子环境对多孔载体的长程骨架结构的重要影响。因此，多相化催化剂的合理设计可以由分子化学规则指导。高效的多相催化剂的概念的基础上多孔聚合物载体和驱动的Hammett参数的联吡啶螯合macroligand在这里证明了Rh催化的光还原二氧化碳的周转频率高达28 h-1，其中最高的多相光催化甲酸生产的报道。
Here we present a series of heterogeneous catalysts based on metal–organic frameworks and microporous polymers used as macroligands for heterogenized organometallic complexes. We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for the Rh-catalyzed photoreduction of carbon dioxide with turnover frequencies up to 28 h–1, among the highest reported for heterogeneous photocatalytic formate production.