Cobalt-Vanadium Bimetallic Heterojunction Stabilizes High-Spin Co³⁺ for Efficient Water Oxidation.

Abstract

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 <i>e</i>_g 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.