Towards superior metal phthalocyanine catalysts for electrochemical oxygen reduction: A comprehensive screening under experimental conditions

Metal phthalocyanines (MPcs) represent a promising class of single-atom catalysts with diverse structures, high thermal stability, and versatile chemical properties. In this work, we have computationally screened nineteen MPcs (metal M = V-Zn, Mo-Ag, and W-Pt ordered based on the atomic number) to assess their suitability as electrochemical oxygen reduction reaction (ORR) catalysts, with consideration of a broad range of experimental conditions, including the oxygen adsorption, temperature effects, partial pressure, solvation effects, pH effects, and demetallation decomposition. Using density functional theory calculations based on the hybrid functional, we find that the ORR behaviors on these MPcs fall into three categories, which are characterized by their distinct oxygen adsorption ability. We correctly predict the experimental ORR performance trend of common MPcs and forecast Rh-, Ir-, Ru-, and MnPc as the four most effective ORR catalysts, outperforming the state-of-the-art FePc in terms of catalytic activity and stability. This study highlights the crucial role of oxygen adsorption, predicts superior MPcs for ORR electrocatalysis, and offers detailed guidance on the optimal working conditions.

Automated summary

In this work, we computationally screened nineteen metal phthalocyanines (MPcs) as electrochemical oxygen reduction reaction (ORR) catalysts, considering a wide range of experimental conditions. Based on density functional theory calculations, we found that these MPcs can be categorized into three groups according to their oxygen adsorption ability. We successfully predicted the experimental ORR performance trend and identified four most effective catalysts, Rh-, Ir-, Ru-, and MnPc, surpassing FePc in terms of catalytic activity and stability. This study highlights the importance of oxygen adsorption and provides guidance for optimal working conditions.