Impact of the Surface Microenvironment on the Redox Properties of a Co-Based Molecular Cathode for Selective Aqueous...

Electrode-confined molecular catalysts are promising systems to enable the efficient conversion of CO₂ to useful products. Here, we describe the development of an original molecular cathode for CO₂ reduction to CO based on the noncovalent integration of a tetraazamacrocyclic Co complex to a carbon nanotube-based matrix. Aqueous electrochemical characterization of the modified electrode allowed for clear observation of a change of redox behavior of the Co center as surface concentration was tuned, highlighting the impact of the catalyst microenvironment on its redox properties. The molecular cathode enabled efficient CO₂-to-CO conversion in fully aqueous conditions, giving rise to a turnover number (TON_CO) of up to 20 × 10³ after 2 h of constant electrolysis at a mild overpotential (η = 450 mV) and with a faradaic efficiency for CO of about 95%. Post operando measurements using electrochemical techniques, inductively coupled plasma, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy characterization of the films demonstrated that the catalysis remained of molecular nature, making this Co-based electrode a new promising alternative for molecular electrocatalytic conversion of CO₂-to-CO in fully aqueous media.