Rapid and efficient electrochemical CO2 reduction is an ongoing challenge for the production of sustainable fuels and other organic molecules. Here, electrochemical CO2 reduction by metalloporphyrin catalysts (metal = Mn, Co, Fe, Ni, Cu) that incorporate a single phenolic group will be discussed. These complexes are minimal versions of related complexes bearing 8 proton relays. A single phenolic group gives rise to robust catalysts for the conversion of CO2-to-CO. CO is the only detected product. TheFe Iron and Co dertiviates are active homogenous catalysts in MeCN solvent. Addition of 1 M water or 8 mM phenol gives rise to almost 100-fold enhancement in turnover frequency. In contrast to the literature, the Fe analogue is a poor catalyst in DMF solvent. These results lead to the proposal of a model where the single phenolic group behaves as a local proton source and hydrogen bonding partner to Brønsted acid additives. The observations from this model suggest improvements for electrocatalytic CO2RR systems.

Proton relays in CO2 reduction catalysts: Is one enough?

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.