Role of crystal structure and electrical polarization of an electrocatalyst in enhancing oxygen evolution performance: Bi-Fe-O system as a case study.

• Orthorhombic Bi 2 Fe 4 O 9 exhibited highest OER activity amongst three Bi-Fe-O. • Lowest charge transfer resistance; highest double-layer capacitance for Bi 2 Fe 4 O 9. • Performance of Bi 2 Fe 4 O 9 attributed to Fe oct -O-Fe td linkages, plate-like morphology. • OER activity increased by factor of 4 after electrical polarization for Bi 25 FeO 40. This work aims to give an insight into the influence of crystal structure (for a system containing same elements but crystallizing in different structures) and the effect of electrical polarization on these oxides on the performance of oxygen evolution reaction (OER). We have tried to highlight this influence by taking the Bi-Fe-O system for the study. Herein, we have synthesized three structures of the Bi-Fe-O system viz. BiFeO 3 (perovskite structure), Bi 2 Fe 4 O 9 (mullite structure), and Bi 25 FeO 40 (sillenite structure) as an example to establish the relation. These oxides were characterized by Rietveld refinement for structure and scanning electron microscopy (SEM) for morphology. Their optical and magnetic properties were also investigated. Systematic studies were carried out with both as-synthesized and electrically polarized oxides for their performance towards OER. We observed that the order for OER activity (using non-polarized catalyst) of the three stable structures synthesized was Bi 2 Fe 4 O 9 > BiFeO 3 > Bi 25 FeO 40 , which was attributed to the presence of Fe (oct) -O-Fe (td) linkages in Bi 2 Fe 4 O 9. While the current density of Bi 2 Fe 4 O 9 and BiFeO 3 remained unchanged after poling, that of Bi 25 FeO 40 increased by four-fold. From the study, we have demonstrated that proper choice of the crystal structure and utilization of electrical polarization can be effective strategies to manipulate the surfaces of an electrocatalytic material. [Display omitted] [ABSTRACT FROM AUTHOR]