Activating Lattice Oxygen in Spinel Oxides via Engineering Octahedral Sites for Oxygen Evolution

作者：Runzhe Chen, Zichen Wang, Suhao Chen, Wei Wu, Yu Zhu, Jun Bo Zhong, Niancai Cheng · 发表于：ACS Energy Letters · 年份：2023 · DOI：10.1021/acsenergylett.3c01030 · 被引用次数：154 · 研究领域：Electrocatalysts for Energy Conversion、Electronic and Structural Properties of Oxides、Advanced Memory and Neural Computing

Spinel oxides, representing an emerging class of highly active catalysts for oxygen evolution (OER), suffer from weak covalency of metal d and oxygen p orbitals from their typical crystal structure, which generally proceeds the OER with an adsorbate evolution mechanism (AEM) pathway. For activating the lattice oxygen in spinel oxides to bypass the scaling relationship limitation of AEM, we herein grow the sulfate salts on the octahedral sites of spinel NiFe 2 O 4 to introduce the Ni 4+ cations and Ni vacancies in octahedral sites, which exhibit remarkable OER performance with an overpotential of 293 mV at 500 mA cm –2 . Experiments and theoretical calculations reveal that the formation Ni 4+ cations and Ni vacancies jointly enhance the metal–oxygen hybridization and strengthen the metal–oxygen bond covalency in both NiFe 2 O 4 and NiFeOOH phases, activating the lattice oxygen and successfully triggering the lattice oxygen mechanism (LOM) pathway on spinel oxides.