Spatial separation strategy to construct N/S co-doped carbon nanobox embedded with asymmetrically coupled Fe-Co pair-site for boosted reversible oxygen electrocatalysis

The fabrication of a remarkably efficient iron-metal-based pair-site, constrained within carbon support, presents a significant and intricate undertaking, primarily attributable to the propensity of proximate metallic entities to amalgamate into the alloy state. In response to this challenge, a spatial segregation approach was conceptualized, aiming to synthesize an N/S co-doped carbon nanobox hosting an asymmetrically coupled Fe-Co pair-site. This engineered nanostructure manifested remarkable electrocatalytic properties, notably featuring a superb half-wave potential of 0.903 V for the oxygen reduction reaction (ORR) and a commendable overpotential of 0.296 V at 10 mA/cm2 for the oxygen evolution reaction (OER). Additionally, a homemade Zn-air battery incorporating this nanohybrid catalyst demonstrated a discharge capacity of 737 mAh/g, a specific maximum power density of 239 mW/cm2 as well as notable durability. Work-function calculations suggested that the electronic interaction between Fe and Co phases, along with the synergetic catalysis of N/S co-doped carbon substrate, could facilitate charge redistribution at the interface, create abundant active sites, and optimize the adsorption-desorption energy of oxygen species on the active center, thus markedly reducing the ORR/OER catalytic reaction barriers. These findings highlight a new strategy for designing and synthesizing efficient bifunctional carbon-based catalysts for energy storage and conversion devices.