Proton Tunneling Distances for Metal Hydrides Formation Manage the Selectivity of Electrochemical CO2 Reduction Reaction

Abstract

AbstractA series of manganese polypyridine complexes were prepared as CO2 reduction electrocatalysts. Among these catalysts, the intramolecular proton tunneling distance for metal hydride formation (PTD‐MH) vary from 2.400 to 2.696 Å while the structural, energetic, and electronic factors remain essentially similar to each other. The experimental and theoretical results revealed that the selectivity of CO2 reduction reaction (CO2RR) is dominated by the intramolecular PTD‐MH within a difference of ca. 0.3 Å. Specifically, the catalyst functionalized with a pendent phenol group featuring a slightly longer PTD‐MH favors the binding of proton to the [Mn−CO2] adduct rather than the Mn center and results in ca. 100 % selectivity for CO product. In contrast, decreasing the PTD‐MH by attaching a dangling tertiary amine in the same catalyst skeleton facilitates the proton binding on the Mn center and switches the product from CO to HCOOH with a selectivity of 86 %.