Facilitating the Deprotonation of OH to O through Fe4+‐Induced States in Perovskite LaNiO3 Enables a Fast Oxygen Evolution Reaction
Year: 2021
Type: article
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 eV. 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.
Source: Small
Institutions: Xiamen University, Collaborative Innovation Center of Chemistry for Energy Materials, University of Cambridge, Nanjing University of Aeronautics and Astronautics, National University of Singapore, Agency for Science, Technology and Research, Institute of Chemical and Engineering Sciences, Queensland University of Technology
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: bronze
Awards: G1033901474, Equipment Account: Integrated Thin Film Deposition and Analysis System, G2175412898, ECCS - EPSRC Development of uniform, low power, high density resistive memory by vertical interface and defect design, Centre for Advanced Materials for Integrated Energy Systems (CAM-IES), Enabling diamond nanoelectronics with metal oxide induced surface doping, 基于过渡金属氧化物单晶薄膜的电子结构与析氧电催化活性构效关系的研究, G3318355, G4576109779, G5000197021, G5200278345, G5200418463, Nanocomposite Oxide Thin Films For Novel Ionotronic Magnetoelectrics, 氧化物/水界面上光、电催化水氧化反应的理论研究, G5513613107, G5909567377, G6236142826, G749247247
OpenAlex ID: W3122188640