氢键有机框架(HOFs)及其应用进展综述

A review of hydrogen-bonded organic frameworks (HOFs) and advances in their applications

  • 摘要: 多孔功能材料在气体储存、生物制药及环境科学等领域受到越来越多的关注。其中,由有机或金属-有机骨架通过分子间氢键自组装而成的氢键有机框架(HOFs)具有结构明确有序,合成条件温和、功能性负载容易等优势,因而受到广泛的重视。HOF可以通过合理选择有机框架分子和调整氢键基序设计定制满足不同应用需求的结构。HOFs中的氢键键能弱于金属有机骨架(MOFs)和共价骨架(COFs)中的共价键和配位键,但它依然具有类似于MOF和COF的灵活组装特性,这激发了各领域研究者们的兴趣。本文主要介绍了以二氨基三嗪(DAT)、羧酸(—COOH)、磺酸(—SO3H)和吡唑(C3H4N2)为代表的四种典型 HOF的合成方法和原理,并从应用角度出发讨论HOF在气体分离、多相催化、电化学应用等领域的最新应用进展,重点关注其在应用稳定性、质子传导、催化、离子筛分及电化学储能方面的表现。此外,我们综述了当前HOF在应用方面的机遇和挑战,为拓宽功能性拓扑多孔材料的应用领域提供有效的参考。

     

    Abstract: Porous functional materials have received increasing attention in fields such as gas storage, biopharmaceuticals and other environmental sciences. Among them, hydrogen-bonded organic frameworks (HOFs), which are self-assembled from organic or metal-organic skeletons through intermolecular hydrogen bonding, have been widely valued because of their well-defined structures, mild synthesis conditions, and ease of functional loading, etc. HOFs can be tailored to meet the needs of different applications by rationally selecting organic framework molecules and adjusting the hydrogen bonding motifs, and the hydrogen bonding energies are weaker than those of metal-organic skeletons (MOFs) and covalent skeletons (COFs). The hydrogen bonding energy in HOFs is weaker than the covalent and coordination bonds in metal-organic frameworks (MOFs) and covalent frameworks (COFs), but they still have flexible assembly properties similar to MOFs and COFs, which has stimulated the interest of researchers in various fields. In this paper, we mainly introduce the synthesis methods and principles of four typical HOFs represented by diaminotriazine (DAT), carboxylic acid (—COOH),sulfonic acid(—SO3H) and pyrazole (C3H4N2), and discuss the latest progress of HOFs in the fields of gas separation, multiphase catalysis, and electrochemical applications from the perspective of applications, focusing on their application stability, proton conduction, catalysis , ion sieving and electrochemical energy storage. In addition, we review the current opportunities and challenges in the application of HOFs to provide an effective reference for broadening the application areas of functional topological porous materials.

     

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