Robust Amide‐Linked Fluorinated Covalent Organic Framework for Long‐Term Oxygen Reduction Reaction Electrocatalysis

Abstract The high energy demand of the evolving world opens the door to develop more sustainable and environmentally friendly energy sources. Oxygen reduction reaction (ORR) is a promising candidate, being the 2e − pathway of great interest for the green production of hydrogen peroxide. Metal‐free covalent organic frameworks (COFs) electrocatalysts present a suitable alternative to substitute the noble‐metals more commonly employed in this application. However, the lability of the linkages building up the framework raises an issue for their long‐term use and application in aggressive media. Herein, a stable amide‐linked COF is reported through post‐synthetic modification of a previously reported imine‐linked COF proven to be effective as an electrocatalyst, enhancing its chemical stability and electrochemical response. It is found that after the linkage transformation, the new electrocatalyst displays a higher selectivity toward the H 2 O 2 production (98.5%) and an enhanced turnover frequency of 0.155 s −1 , which is among the bests reported to date for metal‐free and COF based electrocatalysts. The results represent a promising step forward for metal‐free non pyrolyzed electrocatalysts, improving their properties through post‐synthetic linkage modification for long‐term operation.