High-spin cobalt-based catalysts represent promising candidates for the oxygen evolution reaction (OER) under alkaline conditions. However, during the OER process, the irreversible transformation of the high-spin Co3+(HS-Co3+) species to a low-spin state due to insufficient sustainable electron compensation is a key factor leading to catalyst deactivation. We report a Co2VO4/VN heterojunction exhibiting a three-dimensional layered porous micronanostructure resembling puffed-rice-sphere. The interfacial structure anchored by strong V–N covalent bonds reduce crystal field splitting energy, promotes eg orbitals occupation, and stabilizes HS-Co3+. Concurrently, dynamic charge compensation from the V4+/V5+ redox pair serves as an electron reservoir for Co sites, thereby suppressing the transition to low-spin states. Results demonstrate that the Co2VO4/VN catalyst achieves an ultralow OER overpotential of 253.2 mV at 10 mA·cm–2 in alkaline media, maintaining a stable current density of 1 A cm–2 at 1.866 V for 500 h in 1.0 M KOH. Through a life cycle assessment (LCA) of its preparation and application, the carbon footprint of the catalyst synthesis process is only 48.47 kg CO2-eq This work demonstrates that heterostructure engineering can overcome spin relaxation induced deactivation in high-spin cobalt catalysts, offering a general strategy for designing spin state-tuned electrocatalysts that combine high activity with extended lifetime.
Li et al. (Mon,) studied this question.