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Lanthanide-Driven Electronic and Defect Engineering in Spinel Co3O4: Unraveling the Structure-Activity Synergy for
Tianqi Cao1, Hongyu Cui1, Junyi Liu1
1Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China.
None:
The sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at air cathodes severely restrict the practical application of rechargeable zinc-air batteries (ZABs). Herein, equimolar lanthanide-doped spinel Co3O4 bifunctional electrocatalysts were synthesized via a citric acid-assisted sol-gel method. Among Ce-, Pr-, La-, and Sm-doped catalysts, Sm-Co3O4 exhibits the optimal electrocatalytic performance with a high ORR half-wave potential of 0.72 V and superior OER activity with an overpotential of 1.65 V at 10 mA cm-2, achieving a minimal potential gap ΔE of 0.93 V. Rotating ring-disk electrode (RRDE) measurements and Koutecky-Levich (K-L) analyses confirm the exclusive 4e- ORR pathway. Characterizations reveal that Sm doping modulates the electronic structure and lattice distortion of Co3O4, raises the Co2+/Co3+ ratio (0.59) and creates abundant oxygen vacancies, thereby significantly lowering the overpotentials for both ORR and OER. This study provides new insights for designing high-performance spinel-based bifunctional electrocatalysts for ZABs.
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