中山大学朱克龙团队报道了氮冠醚包埋共价有机框架的制备及其对提高镍锌电池正极性能的影响。相关研究成果于2024年6月20日发表在国际顶尖学术期刊《德国应用化学》。

冠醚（CEs）以其特殊的主客体络合作用而闻名，在共价有机框架（COFs）中作为连接体提供了增强催化和主客体结合性能的潜力。然而，它们的高度柔性构象和低对称性限制了CE衍生的COFs的多样性。

该文中，研究人员介绍了一种新的C3对称氮杂冠醚（ACE）构建块，三（吡啶）[18]冠-6（TPy18C6），用于通过网状合成制备COF（ACE-COF-1和ACE-COF-2）。这种方法能够将CEs精确集成到COFs中，增强Ni²⁺的固定化，同时保持结晶度。所得的Ni²⁺掺杂的COFs(Ni@ACE-COF-1和Ni@ACE-COF-2)在水性碱性镍锌电池中，作为阴极材料表现出高放电容量（在8mA·cm^-2下高达1.27 mAh·cm^-2）和优异的循环稳定性（>1000次循环）。

该项研究是大环化学和网状化学无缝集成的典范，为将大环合成子驱动策略扩展到各种COF构建块奠定了基础，最终生产出适合特定应用的先进材料。

附：英文原文

Title: Fabrication of Azacrown Ether-Embedded Covalent Organic Frameworks for Enhanced Cathode Performance in Aqueous Ni-Zn Batteries

Author: Qing Chen, Mengdi Lin, Xia Li, Zhenglin Du, Yandie Liu, Yisong Tang, Yong Yan, Kelong Zhu

Issue&Volume: 2024-06-20

Abstract: Crown ethers (CEs), known for their exceptional host-guest complexation, offer potential as linkers in covalent organic frameworks (COFs) for enhanced performance in catalysis and host-guest binding. However, their highly flexible conformation and low symmetry limit the diversity of CE-derived COFs. Here, we introduce a novel C3-symmetrical azacrown ether (ACE) building block, tris(pyrido)[18]crown-6 (TPy18C6), for COF fabrication (ACE-COF-1 and ACE-COF-2) via reticular synthesis. This approach enables precise integration of CEs into COFs, enhancing Ni2+ ion immobilization while maintaining crystallinity. The resulting Ni2+-doped COFs (Ni@ACE-COF-1 and Ni@ACE-COF-2) exhibit high discharge capacity (up to 1.27 mAh·cm2 at 8 mA·cm2) and exceptional cycling stability (>1000 cycles) as cathode materials in aqueous alkaline nickel-zinc batteries. This study serves as an exemplar of the seamless integration of macrocyclic chemistry and reticular chemistry, laying the groundwork for extending the macrocyclic-synthon driven strategy to a diverse array of COF building blocks, ultimately yielding advanced materials tailored for specific applications.

DOI: 10.1002/anie.202407575

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202407575