Small | 2021
Facilitating the Deprotonation of OH to O through Fe4+ -Induced States in Perovskite LaNiO3 Enables a Fast Oxygen Evolution Reaction.
Abstract
Aliovalent doping is widely adopted to tune the electronic structure of transition-metal oxides for design of low-cost, active electrocatalysts. Here, using single-crystalline thin films as model electrocatalysts, the structure-activity relationship of Fe states doping in perovskite LaNiO3 for oxygen evolution reaction (OER) is studied. Fe4+ state is found to be crucial for enhancing the OER activity of LaNiO3 , dramatically increasing the activity by six times, while Fe3+ has negligible effect. Spectroscopic studies and DFT calculations indicate Fe4+ states enhance the degree of Ni/Fe 3d and O 2p hybridization, and meanwhile produce down-shift of the unoccupied density of states towards lower energies. Such electronic features reduce the energy barrier for interfacial electron transfer for water oxidization by 0.2\xa0eV. Further theoretical calculations and H/D isotope experiments reveal the electronic states associated with Fe4+ -O2- -Ni3+ configuration accelerate the deprotonation of *OH to *O (rate-determining step), and thus facilitate fast OER kinetics.