羧酸基功能材料在质子传导中的研究进展与展望

Research Progress and Future Prospects of Carboxylic Acid-Based Functional Materials in Proton Conduction

摘要: 质子传导材料作为质子交换膜燃料电池(PEMFCs)的关键核心组件，在推动清洁能源发展方面具有重要的战略地位。本文聚焦于羧酸基功能材料，该类材料凭借其独特的结构可设计性、丰富的氢键网络以及可调控的酸性位点，已成为质子传导领域的研究热点，主要涵盖金属有机框架(MOFs)、共价有机框架(COFs)和氢键有机框架(HOFs)等晶态多孔材料。其中，羧酸基团既可提供质子源，又能通过其氧原子构建连续的氢键网络，协同促进质子传输，其机制主要涉及Grotthuss机制和Vehicle机制。目前，部分材料的质子传导率已接近或达到商业Nafion膜的水平。然而，该领域仍面临三大核心挑战：材料的长期稳定性有待提升，低湿度条件下的传导性能尚需突破，以及结构与性能之间的构效关系亟待深入阐明。本文系统综述了羧酸基功能材料在质子传导领域的研究进展，并展望了其未来发展方向，以期为新型高性能质子传导材料的设计与应用提供参考。

Abstract: Proton-conducting materials, as key components of proton exchange membrane fuel cells (PEMFCs), play a strategically important role in advancing clean energy development. This review focuses on carboxylate-based functional materials, which have emerged as a research hotspot in the field of proton conduction owing to their unique structural designability, rich hydrogen-bonding networks, and tunable acidic sites. These materials primarily encompass crystalline porous frameworks such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and hydrogen-bonded organic frameworks (HOFs). The carboxyl groups not only serve as proton sources but also construct continuous hydrogen-bonding networks through their oxygen atoms, synergistically facilitating proton transport predominantly via the Grotthuss and Vehicle mechanisms. To date, the proton conductivity of some materials has approached or even reached that of the commercial Nafion membrane. However, the field still faces three core challenges: improving the long-term stability of materials, enhancing proton conduction performance under low-humidity conditions, and elucidating the underlying structure-property relationships. This review systematically summarizes the research progress of carboxylate-based functional materials in proton conduction and outlines future development directions, aiming to provide a reference for the design and application of novel high-performance proton-conducting materials.