Anchoring covalent organic polymers on supports with tunable functional groups boosting the oxygen reduction performance under pH-universal conditions

Iron phthalocyanine (FePc) is an attractive nonprecious metal candidate for electrocatalytic oxygen reduction reaction (ORR). However, its low catalytic performance under acidic and neutral conditions limits its practical application. Herein, the FePc-based covalent organic polymers (COPFePc) polymerized in situ on the functionalized multiwalled carbon nanotubes (R-MWCNT) containing different electron-withdrawing or electron-donating groups (COPFePc/R-MWCNT, R = COOH, OH or NH2) were synthesized for ORR. Among them, COPFePc/COOH-MWCNT exhibited the best ORR performance under pH-universal conditions (acidic, neutral, and alkaline). Density-functional theory (DFT) calculations demonstrate that the electron-withdrawing or electron-donating effect of the functional groups in COPFePc/R-MWCNT causes charge redistribution of the active center Fe. The COOH functional group with an electron-withdrawing ability shifts the d-band center of Fe away from the Fermi energy level and reduces the binding strength of oxygen-containing intermediates, accelerating the ORR kinetics and optimizing the catalytic activity.