Reconstruction-Hybridization of Molecular and Metallic Interfaces for Efficient Oxygen Evolution

Abstract

Electrochemical reconstruction of molecular catalysts offers a route to high-performance oxygen evolution reaction (OER) interfaces, but the roles of the molecular centre and substrate in this process remain unclear. Here, we employ a “reconstruction-hybridization” strategy using metal phthalocyanines (M1Pc) as molecular precursors and metal foils (M2) as catalytic hosts. In the FePc/Ni model system, in situ and ex situ characterization reveal that activation transforms Fe–N4 sites to generate a near-surface, disordered, oxygen-coordinated Fe-containing interface on the Ni substrate, which is distinct from bulk oxidation and hence enhances the OER performance by accelerating intermediate adsorption and charge transfer. Systematically screening across M1 and M2 (M1, M2 = Fe, Co, Ni, Cu) establishes the design principle that M1 should possess appropriate redox properties to facilitate interfacial reconstruction while M2 can serve as an active host. The poor performance of the inverse system of NiPc/Fe further supports the non-interchangeable roles of M1 (modulator) and M2 (active host). This work provides mechanistic insight into dynamic interface formation and a general framework for designing efficient multi-metal OER catalysts via electrochemical reconstruction.