Highly Selective Electroreduction of Carbon Dioxide Using Defect-Driven Catalysis

The production of methanol from the electrochemical reduction of CO₂ is a promising method of mitigating climate change while simultaneously producing a useful liquid fuel. In this study, we design self-assembled monolayers (SAMs) of thiols on metal and metal oxide electrodes that operate via cooperative catalysis between the thiolated surface sites and exposed electrode defect sites. This defect-driven mechanism enables the fabrication of SAM-modified ZnO electrodes that yield methanol with an extraordinarily high Faradaic efficiency of up to 92%. To understand the origin of this high selectivity, we study the effect of the chain length of the alkanethiols, different tail functional groups, and applied voltages on catalyst performance. These results combined with density functional theory calculations give a detailed atomic-level understanding of catalyst operation. Furthermore, the SAM linkage tolerates CO₂ reduction conditions, and the catalyst's excellent selectivity for methanol remains high after 10 h of continuous conversion. Taken together, these findings with SAM-based electrodes convey a new and facile design strategy for the creation of highly selective CO₂ reduction electrocatalysts.