受生物启发的界面铁卟啉二聚体，可实现有效的电催化CO2到CO的转化：通过卟啉环上的取代基进行超电势调节。,Scientific Reports

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受生物启发的界面铁卟啉二聚体，可实现有效的电催化CO2到CO的转化：通过卟啉环上的取代基进行超电势调节。
Scientific Reports ( IF 3.8 ) Pub Date : 2016-Apr-18 , DOI: 10.1038/srep24533
Zaki N. Zahran , Eman A. Mohamed , Yoshinori Naruta

将二氧化碳有效地减少为有用的碳资源，特别是二氧化碳，对于开发替代燃料来源和减少二氧化碳的温室效应是必不可少的反应。含Ni，Fe的双核一氧化碳脱氢酶（CODHs）有效催化CO2还原为CO。Ni和Fe的位置适当，可以通过推挽机制协同作用，将CO2转化为CO。受CODH的启发，我们使用了几个具有不同取代基的卟啉二聚体作为合适的配体，以两个具有合适的Fe-Fe分离距离的Fe离子的形式，以高周转频率TOFs有效地和选择性地促进了CO2向CO的转化。卟啉环上的取代基极大地影响了催化过程。通过引入吸电子/给电子基团，例如与引入电子给体的均三基团相比，在卟啉环的所有内消旋位置上，吸电子的全氟苯基的催化超电势η降低了约0.3V。在报道的催化剂中，Fe卟啉二聚体是将CO2转化为CO的最有效的催化剂。对照实验表明，当前的CO2转化为CO的催化剂的高性能归因于在合适的Fe-Fe分离距离处存在双核Fe中心。

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Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings.

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe-containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push-pull mechanism. Bio-inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe-Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe-Fe separation distance.

更新日期：2016-04-20

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