Gao Cunyuan, Zhen Shiyu, Wang Yutong, Wang Lingwei, Cao Yang, Zhan Jinhua, Zhang Liang, Cai Bin
School of Chemistry and Chemical Engineering, Shandong University 250100 Jinan China
Center for Combustion Energy, School of Vehicle and Mobility, State Key Laboratory of Intelligent Green Vehicle and Mobility, Tsinghua University Beijing 100084 China
Chem Sci. 2025 Jan 8;16(5):2429-2436. doi: 10.1039/d4sc06477a. eCollection 2025 Jan 29.
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 Co spin states in ZnCoO 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 Co sites. Increasing the high-spin state of Co 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 Cu, Cd, and Pb. This work provides new insights into the physicochemical determinants of metal ion adsorption, paving the way for advanced sensing technologies and beyond.
了解中间体在界面处的吸附行为对于各种多相体系至关重要，但金属物种受到的关注较少。本研究调查了ZnCoO尖晶石氧化物中Co自旋态的调控，并确定了其对金属离子吸附的影响。以电化学传感为衡量标准，我们揭示了金属离子的吸附亲和力与Co位点的高自旋态分数之间的准线性关系。增加Co的高自旋态会使其d带中心相对于费米能级向下移动，从而减弱金属离子吸附并提高传感性能。这些发现证明了一种自旋态依赖机制，可用于优化与包括Cu、Cd和Pb在内的各种金属物种的相互作用。这项工作为金属离子吸附的物理化学决定因素提供了新的见解，为先进传感技术及其他领域铺平了道路。
