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Effect of a Hydrogen Bond Accepting Microenvironment on Electrocatalytic CO2 Reduction to Formate via Hydride Transfer
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DOI：10.1021/acs.inorgchem.5c00439.png)
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Abstract
En 中文
The rate-determining step in electrochemically driven C–H bond formation with CO2 is often hydride transfer (HT) to the substrate, which is a chemical step that follows the electron transfer (ET) and proton transfer (PT) elementary steps that comprise hydride formation. In the HT step, reaction with protons to give H2 or reaction with CO2 to give formate can occur. The properties of the catalyst-hydride intermediate, along with the characteristics of the reaction solution, will determine both the product selectivity and the overall rate of catalysis. Herein, we characterize and discuss the role of H-bond accepting functional groups on HT. The well-characterized HT catalyst Na(diglyme)2[Fe4N(CO)12] was used for this study along with six derivatives of the cluster that contain H-bond accepting functional groups in the secondary coordination sphere (SCS). We demonstrate that the rate of HT to a substrate, H+ or CO2, directly controls the selectivity for formate vs H2 formation, that there is no direct correlation of the HT rate with H-bond accepting features of the microenvironment, and that the proton source in the reaction solution modulates the observed effects of H-bond accepting SCS. These results illustrate that studies of the H-bond accepting properties of a catalyst microenvironment require consideration of many factors.
Keywords:
hydride transfer
CO2 reduction
formate formation
proton source
hydrogen bonding
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10.5W
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