Designing Bifunctional Oxygen Electrocatalysts Using Prussian Blue Analogue and Carbon Nanostructure Hybrids: Understanding the Role of Individual Components for Oxygen Reduction and Evolution Reactions

Abstract

The incorporation and identification of active sites for OER and ORR is required for designing an efficient bifunctional oxygen electrocatalyst for low cost and high activity of electrochemical devices such as metal air batteries and regenerative fuel cells. In this work, we synthesized CoHCF/GO/f-CNT nanocomposite which showed excellent bi-functional activity with a low overvoltage of 0.8 V between the oxygen evolution reaction (E10 mA/cm 2) and the oxygen reduction reaction (E1/2). The specific functions of CoHCF and GO/f-CNT were described using hydrodynamic voltammetry measurements. For comparison, the pristine CoHCF and the composites with multiwalled carbon nanotubes (CoHCF/f-CNT) and graphene oxide (CoHCF/GO) were also synthesized and thoroughly characterised for physico-chemical and electrochemical properties. It was observed that CoHCF itself had poor ORR activity which increased on addition of GO/f-CNT. Electrochemical analysis suggested that CoHCF is primarily responsible for the OER activity in nanocomposites. The carbon nanostructure, due to strong metal support interactions (SMSI) and electrical conductivity helped in maximising the utilization of PBA active sites on the surface along with acting like a co-catalyst for ORR. The nanoscale geometries of the PBA and GO/CNT further enhanced the metal support and charge transfer interactions, thereby enhancing the activity. The findings of this study provide an insight for developing more effective PBA based nanocomposites for bifunctional OER/ORR electrocatalysis.