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Facilitating the Deprotonation of OH to O through Fe 4+ ‐Induced States in Perovskite LaNiO 3 Enables a Fast Oxygen Evolution Reaction
Author(s) -
Fu Gaoliang,
Li Weiwei,
Zhang JiaYe,
Li Mengsha,
Li Changjian,
Li Ning,
He Qian,
Xi Shibo,
Qi Dongchen,
MacManusDriscoll Judith L.,
Cheng Jun,
Zhang Kelvin Hongliang
Publication year - 2021
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202006930
Subject(s) - lanio , deprotonation , perovskite (structure) , materials science , oxygen evolution , density functional theory , electronic structure , chemistry , catalysis , crystallography , computational chemistry , ion , electrochemistry , biochemistry , optoelectronics , organic chemistry , electrode , dielectric , ferroelectricity
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 LaNiO 3 for oxygen evolution reaction (OER) is studied. Fe 4+ state is found to be crucial for enhancing the OER activity of LaNiO 3 , dramatically increasing the activity by six times, while Fe 3+ has negligible effect. Spectroscopic studies and DFT calculations indicate Fe 4+ states enhance the degree of Ni/Fe 3 d and O 2 p 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 eV. Further theoretical calculations and H/D isotope experiments reveal the electronic states associated with Fe 4+ ‐O 2− ‐Ni 3+ configuration accelerate the deprotonation of *OH to *O (rate‐determining step), and thus facilitate fast OER kinetics.