Activating Octahedral Center in Co‐Doped NiFe2O4 via Bridging Amorphous MoSx for Electrocatalytic Water Oxidation: A Case for eg Orbital Regulation in Spinel Oxide

Author:

Yao Lu1,Wu Xiaofeng1,Zheng Beining2,Liu Jinghai3,Geng Zhibin1,Zhang Yuan1,Cai Minmin1,Shao Zhiyu1,Jiang Mengpei1,Zhang Yaowen1,Chen Yu4,Huang Keke1,Feng Shouhua1ORCID

Affiliation:

1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials College of Chemistry Jilin University Changchun 130012 P. R. China

2. College of Physics Jilin University Changchun 130012 P. R. China

3. Inner Mongolia Key Laboratory of Carbon Nanomaterials Nano Innovation Institute (NII) College of Chemistry and Materials Science Inner Mongolia Minzu University Tongliao Inner Mongolia 028000 P. R. China

4. Shanghai Synchrotron Radiation Facility Shanghai Advanced Research Institute Chinese Academy of Sciences Shanghai 201210 P. R. China

Abstract

AbstractModerate eg filling for octahedral metal cations (MOh) is strongly correlated with the electrocatalytic water oxidation performance in the oxides system. Here, the eg fillings of NiOh and FeOh in NiFe2O4‐based spinel are controllably regulated by introducing an external radical of catalytically inactive MoSx as an electron acceptor via a novel ultrasonic anchored pyrolysis strategy. The electron occupied in eg orbit of MOh emigrates with the amount of MoS hanging on the apical of octahedral sites, and results in a salutary transition from high to medium eg occupancy state, as confirmed by the X‐ray absorption spectroscopy and X‐ray photoelectron spectroscopy. In addition, benefiting from the abundant unsaturated S atoms in amorphous MoSx, the MOh at the surface furthest activates and consequently shows a superior water oxidation performance. Density functional theory also reveals that the eg fillings of Ni and Fe decrease to 1.4 and 1.2 after MoSx modification, which can effectively reduce the free energy of the OOH* intermediates in the oxygen evolution reaction process. This work opens an avenue for further releasing the electrocatalytic activity of octahedral sites through bridging external phases with rational electron‐capturing/donating capability.

Funder

National Natural Science Foundation of China

Publisher

Wiley

Subject

General Materials Science,General Chemistry

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