Spin effects in regulating the adsorption characteristics of metal ions

Abstract

Understanding the adsorption behavior of intermediates at interfaces is crucial for various heterogeneous systems, but less attention has been paid to metal species. This study investigates the manipulation of Co³⁺ spin states in ZnCo₂O₄ spinel oxides and establishes their impact on metal ion adsorption. Using electrochemical sensing as a metric, we reveal a quasi-linear relationship between the adsorption affinity of metal ions and the high-spin state fraction of Co³⁺ sites. Increasing the high-spin state of Co³⁺ shifts its d-band center downward relative to the Fermi level, thereby weakening metal ion adsorption and enhancing sensing performance. These findings demonstrate a spin-state-dependent mechanism for optimizing interactions with various metal species, including Cu²⁺, Cd²⁺, and Pb²⁺. This work provides new insights into the physicochemical determinants of metal ion adsorption, paving the way for advanced sensing technologies and beyond.