Tannic Acid-Induced Morphological and Electronic Tuning of Metal–Organic Frameworks Toward Efficient Oxygen Evolution

This study presents a novel dual-temperature synthesis strategy for cobalt, zinc, and iron-based metal–organic frameworks (MOFs) integrated with tannic acid (TA) surface modification to enhance oxygen evolution reaction (OER) performance. MOFs were synthesized at room temperature and 80 °C, enabling controlled crystal growth and distinct morphologies. Subsequent TA treatment effectively tuned surface chemistry without altering core crystallinity, as confirmed by PXRD, FT-IR, and XPS analyses. Surface modification introduced oxygen-containing functional groups, improved charge transfer, and increased active-site accessibility. Among the catalysts, the tannic acid-modified Fe-based MOF synthesized at 80 °C (TAFeM-2) exhibited outstanding OER activity, achieving an overpotential of only 254 mV at 10 mA cm−2, outperforming benchmark RuO2 (276 mV) and unmodified counterparts. Tafel slope analysis revealed faster reaction kinetics for surface-tuned MOFs, while electrochemical impedance spectroscopy indicated reduced charge-transfer resistance (12 Ω for TAFeM-2). Chronoamperometry demonstrated exceptional long-term stability, maintaining constant current density over 20 h with minimal performance loss. Post-OER characterization suggested surface oxidation to iron oxyhydroxides without significant structural degradation. This work demonstrates that combining dual-temperature synthesis with TA surface engineering yields MOF-based catalysts with superior activity, conductivity, and durability, offering a promising pathway for developing high-performance electrocatalysts for sustainable energy applications.