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Updated: Aug 28, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Metal-free redox active covalent organic frameworks for electrocatalytic oxygen reduction reaction
Bikash Mishra1, Surajit Samui2, Sourav Ghosh3
1Department of Chemical and Biological Sciences, S. N. Bose National Centre for Basic Sciences, Kolkata - 700106, India.
Abstract:
Designing efficient, metal-free covalent organic framework (COF) electrocatalysts is a promising strategy for the oxygen reduction reaction (ORR) due to their structural tunability and stability. Herein, we report two redox-active donor-acceptor COFs, TAPA-DHTD and TTT-DHTD, incorporating a thiophene-based dithiophenedione (DHTD) unit. Among them, TTT-DHTD exhibits superior ORR performance with a half-wave potential (E1/2) of 0.82 V vs RHE, approaching that of 20% Pt/C (0.85 V) and surpassing most reported metal-free COFs. It also demonstrates excellent methanol tolerance and long-term durability, maintaining activity over 120 hours. Density functional theory (DFT) calculations reveal that the donor-acceptor framework optimizes the p-band center, enhances charge separation, and improves adsorption of oxygenated intermediates, thereby accelerating ORR kinetics. This work provides a rational strategy for designing durable, high-performance metal-free electrocatalysts for sustainable energy applications.
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