| 马奥,李娟,宋登科,王惠峰,曹长青,樊燕鸽.化学通报,2026,89(6):662-676. |
| 离子型共价有机框架材料的结晶度调控策略与应用进展 |
| Crystallinity Control Strategies and Application Advances in Ionic Covalent Organic Frameworks |
| 投稿时间：2026-01-27 修订日期：2026-03-17 |
| DOI： |
| 中文关键词: 离子型共价有机框架 离子化 多孔材料 结晶度 |
| 英文关键词:ionic covalent organic frameworks ionization porous materials crystallinity |
| 基金项目:河南省高端外国专家项目（HNGDB2026008）和郑州市外国专家工作室项目（ZZGZS2024009）资助 |
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| 中文摘要: |
| 离子型共价有机框架材料（iCOF）作为共价有机框架材料（COF）的重要分支，通过引入带电基团赋予材料独特的静电相互作用与离子交换能力，广泛应用于吸附、催化、传导、分离及生物医学等领域。然而，其结晶度的不足严重制约了其长程有序结构与性能的充分发挥。本文针对iCOF合成中带电基团引发的静电排斥与结晶有序性的问题，系统梳理并归纳了iCOF结晶度调控的三大核心策略：动态共价化学平衡调控策略、拓扑结构与分子工程预调控策略和分步合成与过程调控策略，阐明了各类策略的原理、实施路径与调控效果，深入探讨了结晶度对iCOF吸附、催化、质子传导、电化学等性能的影响，旨在为未来高性能iCOF的设计与合成提供系统性的理论依据和技术参考。 |
| 英文摘要: |
| Ionic covalent organic frameworks (iCOFs), as a pivotal subclass of covalent organic frameworks (COFs), are endowed with unique electrostatic interactions and ion exchange capacity via the incorporation of charged moieties, and have been extensively employed in a wide range of fields including adsorption, catalysis, ion conduction, separation, and biomedicine. However, the insufficient crystallinity of iCOFs severely hinders the full exploitation of their long-range ordered structures and corresponding functionalities. Herein, targeting the intrinsic conflict between the electrostatic repulsion induced by charged moieties and crystalline ordering during the synthesis of iCOFs, we systematically summarize three core strategies for the crystallinity regulation of iCOFs, namely the equilibrium regulation strategy based on dynamic covalent chemistry, the pre-regulation strategy via topology design and molecular engineering, and the stepwise synthesis and process control strategy. The working principles, implementation approaches, and regulation outcomes of each strategy are systematically elucidated, and the critical impacts of crystallinity on the key performances of iCOFs in adsorption, catalysis, proton conduction, and electrochemical applications are thoroughly discussed. This review aims to provide a systematic theoretical foundation and technical reference for the rational design and controllable synthesis of high-performance iCOFs in future research. |
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