Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction,Journal of the American Chemical Society

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Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-01-16 , DOI: 10.1021/jacs.7b11940
Christian S. Diercks , Song Lin ₁ , Nikolay Kornienko , Eugene A. Kapustin , Eva M. Nichols , Chenhui Zhu , Yingbo Zhao , Christopher J. Chang , Omar M. Yaghi

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The electronic character of porphyrin active sites for electrocatalytic reduction of CO2 to CO in a two-dimensional covalent organic framework (COF) was tuned by modification of the reticular structure. Efficient charge transport along the COF backbone promotes electronic connectivity between remote functional groups and the active sites and enables the modulation of the catalytic properties of the system. A series of oriented thin films of these COFs was found to reduce CO2 to CO at low overpotential (550 mV) with high selectivity (faradaic efficiency of 87%) and at high current densities (65 mA/mg), a performance well beyond related molecular catalysts in regard to selectivity and efficiency. The catalysts are stable for more than 12 h without any loss in reactivity. X-ray absorption measurements on the cobalt L-edge for the modified COFs enable correlations between the inductive effects of the appended functionality and the electronic character of the reticulated molecular active sites.

中文翻译：

用于电催化二氧化碳还原的共价有机骨架中卟啉活性位点的网状电子调谐

在二维共价有机骨架 (COF) 中，卟啉活性位点的电子特性可通过网状结构的修饰来调节，用于将 CO2 电催化还原为 CO。沿着 COF 主链的有效电荷传输促进了远程官能团和活性位点之间的电子连接，并能够调节系统的催化性能。发现这些 COF 的一系列定向薄膜在低过电位 (550 mV) 和高选择性（法拉第效率为 87%）和高电流密度（65 mA/mg）下将 CO2 还原为 CO，其性能远远超过相关的分子催化剂的选择性和效率。催化剂稳定超过 12 小时，反应性没有任何损失。

更新日期：2018-01-16

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