Binuclear Metal Phthalocyanines with Enhanced Activity in the Oxygen Evolution Reaction: A First-Principles Study

Abstract

The rational design of efficient catalysts for the electrochemical oxygen evolution reaction (OER) critically relies on a comprehensive understanding of the reaction mechanisms. Herein, the alkaline OER on planar mononuclear metal phthalocyanines (MPc, where M = Mn, Co, Fe, and Ni) and binuclear metal phthalocyanines (bi-MPc) is studied using density functional theory (DFT) methods. Both FePc and bi-CoPc exhibit enhanced stability and OER activity, with the energy required for the leaching of central metal being as high as 2.28 and 2.45 eV and the overpotentials of the OER being 0.48 and 0.57 V, respectively. Through electronic structure analysis, it is found that, in the OER process of bi-MPc, the large macrocyclic ligand and metal ions not bonding with the intermediate can serve as hole reservoirs. Intermediate species are further stabilized by the dispersal of a positive charge, reducing the free energy. These findings underscore the significance of macrocyclic ligands in the rate-determining step of the OER catalyst.