Directional Manipulation of Electron Transfer by Energy Level Engineering for Efficient Cathodic Oxygen Reduction

Nano Lett. 2022 Aug 24;22(16):6622-6630. doi: 10.1021/acs.nanolett.2c01933. Epub 2022 Aug 5.

Abstract

Electron transfer plays an important role in determining the energy conversion efficiency of energy devices. Nitrogen-coordinated single metal sites (M-N4) materials as electrocatalysts have exhibited great potential in devices. However, there are still great difficulties in how to directionally manipulate electron transfer in M-N4 catalysts for higher efficiency. Herein, we demonstrated the mechanism of electron transfer being affected by energy level structure based on classical iron phthalocyanine (FePc) molecule/carbon models and proposed an energy level engineering strategy to manipulate electron transfer, preparing high-performance ORR catalysts. Engineering molecular energy level via modulating FePc molecular structure with nitro induces a strong interfacial electronic coupling and efficient charge transfer from carbon to FePc-β-NO2 molecule. Consequently, the assembled zinc-air battery exhibits ultrahigh performance which is superior to most of M-N4 catalysts. Energy level engineering provides a universal approach for directionally manipulating electron transfer, bringing a new concept to design efficient and stable M-N4 electrocatalyst.

Keywords: Zn-air battery; directional electron transfer; energy level design; oxygen reduction reaction.