Kinetic Insights into the Mechanism of Oxygen Reduction Reaction on Fe2O3 /C Composites

Abstract

Electrochemical energy storage and conversion systems are the appealing replacement for nonrenewable resources to provide clean and sustainable energy. Of particular interest are fuel cells and metal-air batteries, both of which rely on the oxygen reduction reaction (ORR) for their operation. Fe-N-C catalyst has been widely used as a prominent catalyst towards ORR, but there is still some ambiguity regarding its active sites. This study describes the role of Fe2O3, an inevitable species formed in Fe-N-C catalyst towards the ORR. The Fe2O3 is carefully synthesised on various carbon supports and characterised using XPS spectra, HRTEM images, and surface area analysis. The particle size of the Fe2O3 nanoparticles synthesised on the pores of the carbon support was determined to be ~10 nm from the HRTEM analysis. The current density of ORR and the number of electrons transferred on Fe2O3/C catalysts is increased compared with bare carbon supports. Based on the kinetic analysis, the ORR on Fe2O3/C follows pseudo-4-electron (or) 2+2-electron ORR, where the first 2-electron ORR to H2O2 and second 2-electron H2O2 reduction reaction (HPRR) to H2O are assigned to the graphitic carbon (carbon defects) and Fe2O3 active sites, respectively. The role of Fe2O3 is further studied using the Theoretical method, which reveals the decreased formation of free energy of O2 adsorption. The Fe2O3 reduces the energy barrier for the reduction of *OOH to OH-. The Fe2O3/C shows higher stability by retaining 95% of the initial activity even after 20,000 cycles. Figure 1