LAUSR

The effects of primary and second coordination spheres on molecular electrocatalysis have been extensively studied, yet investigations of third functional spheres are rarely reported. Here we report an electrocatalyst (ZnPEG8T) with a hydrophilic channel as a third functional sphere that facilitates relay proton shuttling to the primary and second coordination spheres for enhanced catalytic CO2 reduction. Using foot-of-the-wave analysis, the ZnPEG8T catalyst displayed CO2-to-CO activity (TOFmax) thirty times greater than that of the benchmark catalyst without a third functional sphere. A kinetic isotopic effect (KIE) study, in conjunction with voltammetry and UV-Visible spectroscopy, uncovered that the rate limiting step is not the protonation step of the metallocarboxylate intermediate, as observed in many other molecular CO2 reduction electrocatalysts, but rather the replenishment of protons in the proton shuttling channel. Controlled-potential electrolysis using ZnPEG8T displayed a Faradaic efficiency of 100% for CO2-to-CO conversion at -2.4 V vs Fc/Fc+. A Tafel plot was also generated for a comparison to other reported molecular catalysts. This report validates a strategy for incorporating higher functional spheres for enhanced catalytic efficiency in proton-coupled electron transfer reactions.