Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

Iron phthalocyanine (FePc) is a promising non-precious catalyst for the oxygen reduction reaction (ORR). Unfortunately, FePc with plane-symmetric FeN(4) site usually exhibits an unsatisfactory ORR activity due to its poor O(2) adsorption and activation. Here, we report an axial Fe–O coordination induced electronic localization strategy to improve its O(2) adsorption, activation and thus the ORR performance. Theoretical calculations indicate that the Fe–O coordination evokes the electronic localization among the axial direction of O–FeN(4) sites to enhance O(2) adsorption and activation. To realize this speculation, FePc is coordinated with an oxidized carbon. Synchrotron X-ray absorption and Mössbauer spectra validate Fe–O coordination between FePc and carbon. The obtained catalyst exhibits fast kinetics for O(2) adsorption and activation with an ultralow Tafel slope of 27.5 mV dec(−1) and a remarkable half-wave potential of 0.90 V. This work offers a new strategy to regulate catalytic sites for better performance.