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Vanadium Cation Exchange-Driven Reconstruction of MOF-Derived Cobalt Hydroxide Electrodes for Electrocatalysis and
Yongbeen Kim1, Seungwoo Han1, Wonyoung Lee1,2
1School of Mechanical Engineering, Sungkyunkwan University (SKKU), Suwon, Republic of Korea.
Abstract:
The development of earth-abundant oxygen evolution reaction (OER) electrocatalysts remains challenging because structural reconstruction and electronic/defect modulation are often addressed separately. Herein, a room-temperature vanadium cation exchange strategy that enables structural reconstruction and electronic/defect modulation is reported. Vanadium cation exchange removes organic ligands and drives the phase transformation to mesoporous cobalt hydroxide using ZIF-67 grown on nickel foam, while high-valence vanadium incorporation increases the cobalt oxidation state and promotes oxygen vacancy formation. The optimized V20-Co(OH)2 electrode exhibits current densities of 50 mA cm-2 and 100 mA cm-2 at overpotentials of 268 and 293 mV, respectively, in 1.0 M KOH, and maintains stable operation for 150 h. In situ Raman and post-stability analyses reveal the formation of a CoOOH-like active surface during OER operation, while oxygen vacancy-related features and a high cobalt oxidation state are largely retained after operation. Spectroscopic, electrochemical, and kinetic analyses reveal an increased contribution from lattice oxygen participation during OER. The defect-engineered electrode exhibits enhanced performance in supercapacitors and zinc-air batteries, demonstrating a generalizable electrode engineering strategy for energy storage and conversion systems.
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