Tuning the Electrocatalytic Activity of Co₃O₄ through Discrete Elemental Doping

To gain constructive insight into the possible effect of doping on the electrocatalytic activity of materials, a catalytic framework with a discrete distribution of dopants is an appropriate model system. Such a system assures well-defined active centers, maximum atom utilization efficiency, and hence enhanced selectivity, catalytic activity, and stability. Herein, a comprehensive investigation of the electrocatalytic activity of iron-doped cobalt oxide (Fe-Co₃O₄) nanosheets is presented. In order to understand the contribution of dopants, a series of materials with controlled doping levels are investigated. By controlled iron inclusion into the structure of Co₃O₄, an apparent improvement in the oxygen evolution reaction activity which is reflected in the decrease of 160 mV in the overpotential to reach the current density of 10 mA/cm² is manifested. Additionally, it is shown that there exists an optimum doping content above which the catalytic activity fades. Further investigation of the system with density functional calculations reveals that, along with the optimization of adsorption energy toward the reaction intermediates, substantial downshift of the Fermi level and delocalization of electron density occurs on introducing iron ions into the structure.