Coordination Engineering of Defective Cobalt-Nitrogen-Carbon Electrocatalysts with Graphene Quantum Dots for Boosting...

Developing efficient and robust metal-nitrogen-carbon electrocatalysts for oxygen reduction reaction (ORR) is of great significance for the application of hydrogen-oxygen fuel cells and metal-air batteries. Herein, a coordination engineering strategy is developed to improve the ORR kinetics and stability of cobalt-nitrogen-carbon (Co-N-C) electrocatalysts by grafting the oxygen-rich graphene quantum dots (GQDs) onto the zeolite imidazole frameworks (ZIFs) precursors. The optimized oxygen-rich GQDs-functionalized Co-N-C (G-CoNOC) electrocatalyst demonstrates an increased mass activity, nearly two times higher than that of pristine defective Co-N-C electrocatalyst, and retains a stability of 90.0% after 200 h, even superior to the commercial Pt/C. Comprehensive investigations demonstrate that the GQDs coordination can not only decrease carbon defects of Co-N-C electrocatalysts, improving the electron transfer efficiency and resistance to the destructive free radicals from H₂ O₂ , but also optimize the electronic structure of atomic Co active site to achieve a desired adsorption energy of OOH^- , leading to enhanced ORR kinetics and stability by promoting further H₂ O₂ reduction, as confirmed by theoretical calculations and experimental results. Such a coordination engineering strategy provides a new perspective for the development of highly active noble-metal-free electrocatalysts for ORR.