Electronic π-delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets,Journal of the American Chemical Society

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Electronic π-delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-05 , DOI: 10.1021/jacs.7b06828
Pablo Garrido-Barros _{1,

2} , Carolina Gimbert-Suriñach ₁ , Dooshaye Moonshiram ₁ , Antonio Picón _{3,

4} , Pere Monge ₁ , Victor S. Batista ₅ , Antoni Llobet _{1,

6}

Affiliation

A molecular water oxidation catalyst based on the copper complex of general formula [(Lpy)CuII]2-, 22-, (Lpy is 4-pyrenyl-1,2-phenylenebis(oxamidate) ligand) has been rationally designed and prepared to support a more extended π-conjugation through its structure in contrast with its homologue, the [(L)CuII]2- water oxidation catalyst, 12- (L is o-phenylenebis(oxamidate)). The catalytic performance of both catalysts has been comparatively studied in homogeneous phase and in heterogeneous phase by π-stacking anchorage to graphene-based electrodes. In the homogeneous system, the electronic perturbation provided by the pyrene functionality translates into a 150 mV lower overpotential for 22- with respect to 12- and an impressive increase in the kcat from 6 to 128 s-1. Upon anchorage, π-stacking interactions with the graphene sheets provide further π-delocalization that improves the catalytic performance of both catalysts. In this sense, 22- turned out to be the most active catalyst due to the double influence of both the pyrene and the graphene, displaying an overpotential of 538 mV, a kcat of 540 s-1 and producing more than 5300 TONs.

中文翻译：

电子 π-离域化通过在石墨烯片上异质化的 Cu(II) 分子催化剂促进催化水氧化

合理设计并制备了一种基于通式[(Lpy)CuII]2-, 22-, (Lpy 是4-芘基-1,2-亚苯基双(草酰胺)配体)的铜配合物的分子水氧化催化剂以支持与其同系物 [(L)CuII]2- 水氧化催化剂 12-（L 是邻亚苯基双（草酰胺））相比，通过其结构具有更扩展的 π 共轭。两种催化剂在均相和非均相中的催化性能通过 π 堆积锚定在石墨烯基电极上进行了比较研究。在均相系统中，芘官能团提供的电子扰动转化为 22- 相对于 12- 的过电位降低了 150 mV，kcat 从 6 s-1 显着增加到 128 s-1。锚泊时，与石墨烯片的 π 堆积相互作用提供了进一步的 π 离域，从而提高了两种催化剂的催化性能。从这个意义上说，由于芘和石墨烯的双重影响，22- 被证明是最活跃的催化剂，显示出 538 mV 的过电位，540 s-1 的 kcat 并产生超过 5300 吨。

更新日期：2017-09-05

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