Enhanced Molecular CO₂ Electroreduction Enabled by a Flexible Hydrophilic Channel for Relay Proton Shuttling

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, an electrocatalyst (ZnPEG8T) was developed 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 (TOF_max ) 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/Vis spectroscopy, uncovered that the rate-limiting step was 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.