Asymmetric Push–Pull Type Co(II) Porphyrin for Enhanced Electrocatalytic CO(2) Reduction Activity

Molecular electrocatalysts for electrochemical carbon dioxide (CO(2)) reduction has received more attention both by scientists and engineers, owing to their well-defined structure and tunable electronic property. Metal complexes via coordination with many π-conjugated ligands exhibit the unique electrocatalytic CO(2) reduction performance. The symmetric electronic structure of this metal complex may play an important role in the CO(2) reduction. In this work, two novel dimethoxy substituted asymmetric and cross-symmetric Co(II) porphyrin (PorCo) have been prepared as the model electrocatalyst for CO(2) reduction. Owing to the electron donor effect of methoxy group, the intramolecular charge transfer of these push–pull type molecules facilitates the electron mobility. As electrocatalysts at −0.7 V vs. reversible hydrogen electrode (RHE), asymmetric methoxy-substituted Co(II) porphyrin shows the higher CO(2)-to-CO Faradaic efficiency (FE(CO)) of ~95 % and turnover frequency (TOF) of 2880 h(−1) than those of control materials, due to its push–pull type electronic structure. The density functional theory (DFT) calculation further confirms that methoxy group could ready to decrease to energy level for formation *COOH, leading to high CO(2) reduction performance. This work opens a novel path to the design of molecular catalysts for boosting electrocatalytic CO(2) reduction.