| Autor: |
Gonell S; Department of Chemistry , University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599-3290 , United States., Massey MD; Department of Chemistry , University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599-3290 , United States., Moseley IP; Department of Chemistry , University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599-3290 , United States., Schauer CK; Department of Chemistry , University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599-3290 , United States., Muckerman JT; Chemistry Division , Brookhaven National Laboratory , P.O. Box 5000, Upton , New York 11973-5000 , United States., Miller AJM; Department of Chemistry , University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599-3290 , United States. |
| Abstrakt: |
A comprehensive mechanistic study of electrocatalytic CO 2 reduction by ruthenium 2,2':6',2″-terpyridine (tpy) pyridyl-carbene catalysts reveals the importance of stereochemical control to locate the strongly donating N-heterocyclic carbene ligand trans to the site of CO 2 activation. Computational studies were undertaken to predict the most stable isomer for a range of reasonable intermediates in CO 2 reduction, suggesting that the ligand trans to the reaction site plays a key role in dictating the energetic profile of the catalytic reaction. A new isomer of [Ru(tpy)(Mebim-py)(NCCH 3 )] 2+ (Mebim-py is 1-methylbenzimidazol-2-ylidene-3-(2'-pyridine)) and both isomers of the catalytic intermediate [Ru(tpy)(Mebim-py)(CO)] 2+ were synthesized and characterized. Experimental studies demonstrate that both isomeric precatalysts facilitate electroreduction of CO 2 to CO in 95/5 MeCN/H 2 O with high activity and high selectivity. Cyclic voltammetry, infrared spectroelectrochemistry, and NMR spectroscopy studies provide a detailed mechanistic picture demonstrating an essential isomerization step in which the N-trans catalyst converts in situ to the C-trans variant. Insight into molecular electrocatalyst design principles emerge from this study. First, the use of an asymmetric ligand that places a strongly electron-donating ligand trans to the site of CO 2 binding and activation is critical to high activity. Second, stereochemical control to maintain the desired isomer structure during catalysis is critical to performance. Finally, pairing the strongly donating pyridyl-carbene ligand with the redox-active tpy ligand proves to be useful in boosting activity without sacrificing overpotential. These design principles are considered in the context of surface-immobilized electrocatalysis. |
