固体核磁共振新方法的开发及其在顺磁性金属有机框架型电池材料表征中的应用

金属有机框架基于其结构多样性、多孔性等特点，在气体存储与分离、催化、电化学储能与转换等领域展现出了潜在的应用前景。固体核磁共振技术是表征该类多孔材料的重要手段。本项目以揭示顺磁性金属有机框架材料作为电池电极材料的充放电机理为科学研究目标，着重开发高转速条件下的新型固体NMR方法，以克服传统固体NMR方法在表征该体系时的若干缺陷。本课题拟开发13C、14N的宽带激发与检测、空间相邻性（1H-13C、1H-14N）检测的新方法，尤其是14N overtone跃迁信号的宽频直接与间接检测新方法。新开发的方法有助于我们对顺磁性金属有机框架的宽频谱学信号进行明确的归属，并且帮助我们从分子和原子水平上揭示金属有机框架电极材料在充放电过程中局域微观化学环境的变化，为新型高性能锂、钠电池电极材料的开发提供理论依据。

Metal-Organic Frameworks have shown potential applications in various fields, such as gas storage and separation, catalyst, electrochemical energy storage and conversion, due to their structural diversity and porosity. Solid-State NMR is a vital tool for characterizations of this type porous material. This program, targeting at the detailed charge-discharge mechanism of paramagnetic MOF when applied as electrode materials in batteries, will focus on developing new SSNMR methods under ultra-fast MAS condition to overcome the drawbacks of traditional methods. We will be mainly working on designing new SSNMR methods for broadband excitation and detection of 13C and 14N, methods for probing 1H-13C and 1H-14N proximities, and especially the broadband indirectly and directly detection of 14N overtone transitions. These new methods will permit the unambiguous assignment of broadband NMR signals of paramagnetic MOFs. Moreover, changes of local environments can be probed during charging and discharging processes at the molecule and atom level, which would provide fundamental basis for developing novel high-performance lithium and sodium-battery electrode materials.