Regio-isomerism directed electrocatalysis for energy efficient zinc-air battery

We have investigated the role of ligand isomerism in modulating the mechanisms and kinetics associated with charge/discharge chemistry of an aqueous metal-air battery. The dominant electron-withdrawing inductive effect (-I effect) and the diminished electron-withdrawing resonance effect (-R effect) in the α-NO₂ isomer noticeably diminishes the rate of oxygen reduction (ORR) and oxygen evolution reactions (OER) on the catalytic Co-center. In their β-counterpart, the cumulative -I and -R effects noticeably enhance the OER and ORR kinetics on the same catalytic Co-center. Therefore, the regioisomerism of the -NO₂ functionality amplifies the kinetics of ORR/OER without influencing their mechanistic pathways. When isomeric electrocatalysts are integrated to aid the charge chemistry of a Zn-air battery, the overpotential could be decreased by ∼250 mV with β-NO₂ isomer leading to a round-trip efficiency as high as 60%. This work contributes to the design of novel molecular platforms to target the overall round-trip efficiency of energy storage and conversion devices.