Liu Feng, Shi Lei, Lin Xuanni, Zhang Biao, Long Yongde, Ye Fenghui, Yan Riqing, Cheng Ruyi, Hu Chuangang, Liu Dong, Qiu Jieshan, Dai Liming
State Key Laboratory of Organic-Inorganic Composites, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
Institute of Materials Science and Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, China.
Sci Adv. 2023 Jun 9;9(23):eadg0366. doi: 10.1126/sciadv.adg0366.
Here, we report a conceptual strategy for introducing spatial sulfur (S)-bridge ligands to regulate the coordination environment of Fe-Co-N dual-metal centers (Spa-S-Fe,Co/NC). Benefiting from the electronic modulation, Spa-S-Fe,Co/NC catalyst showed remarkably enhanced oxygen reduction reaction (ORR) performance with a half-wave potential () of 0.846 V and satisfactory long-term durability in acidic electrolyte. Combined experimental and theoretical studies revealed that the excellent acidic ORR activity with a remarkable stability observed for Spa-S-Fe,Co/NC is attributable to the optimal adsorption-desorption of ORR oxygenated intermediates achieved through charge-modulation of Fe-Co-N bimetallic centers by the spatial S-bridge ligands. These findings provide a unique perspective to regulate the local coordination environment of catalysts with dual-metal-centers to optimize their electrocatalytic performance.
在此，我们报告了一种引入空间硫（S）桥连配体以调控Fe-Co-N双金属中心（Spa-S-Fe,Co/NC）配位环境的概念策略。得益于电子调制，Spa-S-Fe,Co/NC催化剂展现出显著增强的氧还原反应（ORR）性能，其半波电位（）为0.846 V，且在酸性电解质中具有令人满意的长期耐久性。结合实验和理论研究表明，Spa-S-Fe,Co/NC所观察到的具有卓越稳定性的优异酸性ORR活性归因于通过空间S桥连配体对Fe-Co-N双金属中心进行电荷调制而实现的ORR含氧中间体的最佳吸附-解吸。这些发现为调控双金属中心催化剂的局部配位环境以优化其电催化性能提供了独特视角。
