Journal
CHEMICAL ENGINEERING JOURNAL
Volume 417, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2021.129324
Keywords
Perovskite oxide; Oxygen evolution; Lattice oxygen mechanism; DFT; High entropy
Categories
Funding
- National Natural Science Foundation of China [21773195]
- National Key Research and Development Program [2019YFD0901105]
- Guangdong Basic and Applied Basic Research Foundation [2020A1515110904]
- National Science Foundation of Fujian Province, China [2018J01062]
- Indiana State University
- Xiamen University
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University
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Through co-incorporation of Fe/Mn elements, the designed perovskite cobaltate nanofiber LSCFM significantly enhances the participation of lattice oxygen in the oxygen evolution reaction (OER) process, resulting in lower overpotential and Tafel slope. Experimental and theoretical approaches further unveil the strongest pH-dependent activity and metal-oxygen covalency on LSCFM.
Lattice oxygen-mediated mechanism (LOM) on perovskite oxides for oxygen evolution reaction (OER) process has revealed kinetic superiority over conventional adsorbate evolution mechanism (AEM). However, feasibly enhancing the participation of lattice oxygen is still challenging. Here we designed a perovskite cobaltate (La0.6Sr0.4Co0.8Fe0.1Mn0.1O3-delta, LSCFM) nanofiber, and discovered that the co-incorporation of Fe/Mn elements significantly intensifies the involvement of lattice oxygen for OER. Compared with its mono-dopant (Fe or Mn only) counterparts, the LSCFM gives rise to higher surface oxygen vacancies (V-o) concentration and faster oxygen ion diffusion coefficient, endowing a small overpotential of 343 mV at 10 mA cm(-2) and low Tafel slope of 63 mV dec(-1). The strongest pH-dependent activity and metal-oxygen covalency are further unveiled on LSCFM by experimental and theoretical approaches, evidencing that the promoted OER kinetics on LSCFM predominantly stems from the formation of reactive lattice oxygen site.
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