Engineered Cobalt Single-Atoms@BiFeO3 Heteronanostructures for Highly Efficient Solar Water Oxidation

Efficient charge–carrier separation and their utilization are the key factors in overcoming sluggish four-electron reaction kinetics involved in photocatalytic oxygen evolution. Here, a novel study demonstrates the significance of Na₂S₂O₈ as a sacrificial agent in comparison to AgNO₃. Resultantly, BiFeO₃ (BFO) and titanium doped-oxygen deficient BiFeO₃ (Ti-BFO-R) nanostructures achieve ≈64 and 44.5 times higher O₂ evolution in the presence of Na₂S₂O₈ compared to AgNO₃ as a sacrificial agent, respectively. Furthermore, the presence of Co single atoms (Co-SAs) deposited via immersion method on BFO and Ti-BFO-R nanostructures led to achieving outstanding O₂ evolution at a rate of 16.11 and 23.89 mmol g⁻¹ h⁻¹, respectively, which is 153 and 227.5 times higher compared to BFO (in the presence of AgNO₃), the highest O₂ evolution observed for BFO-based materials to date. The successful deposition of Co-SAs is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC HAADF-STEM) and X-ray absorption near-edge structure (XANES). The charge transfer investigations confirm the significance of Co-SAs on BFO-based photocatalysts for improved charge–carrier separation, transport, and utilization. This novel study validates the excellent role of Na₂S₂O₈ as a sacrificial agent and Co-SAs as a cocatalyst for BFO-based nanostructures for efficient O₂ evolution.