Tuning the Electrochemical Property of the Ultrafine Metal‐oxide Nanoclusters by Iron Phthalocyanine as Efficient Catalysts for Energy Storage and Conversion.

Nanoclusters (NCs) have been demonstrated of outstanding performance in electrochemical energy storage and conversion technologies due to their strong quantum confinement effects and strong interaction with supports. Here, we developed a class of ultrafine metal‐oxide (MOx, M = Fe, Co and Ni) NCs incorporated with iron phthalocyanine (FePc), MOx/FePc‐G, supported on graphene as high‐performance catalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and carbon dioxide reduction (CO2RR). The high activities for ORR and OER are attributed to the electron donation and accepting ability of the highly redox active of FePc‐G that could tune the properties of MOx. The FeOx/FePc‐G exhibits an extremely positive half‐wave potential (E1/2) of 0.888 and 0.610 V for ORR in alkaline and neutral conditions, respectively, which is around 60 mV more positive than that of Pt/C. And NiOx/FePc‐G shows similar OER activity with the state‐of‐the‐art catalysts, Ir/C, and better performance than NiFeO NCs supported on graphene. Remarkably, the CoOx/FePc‐G and NiOx/FePc‐G show high activity and selectivity to reduce CO2 into CO with a low onset potential of −0.22 V (overpotential is 0.11 V). The ultrafine metal‐oxide nanoclusters can be tuned by the closely adjacent iron phthalocyanine (FePc), and the high electron flexibility of the FePc could assist the electrons transfer process for oxygen reduction, oxygen evolution, and carbon dioxide reduction. [ABSTRACT FROM AUTHOR]