The design of new types of proton-conductive materials with high proton conductivity has sparked tremendous interest. Covalent organic framework (COF), a new category of porous crystalline materials possessing well-defined porosity and tunable functionality, holds great potential as next-generation proton conductors. Here, triazole COF loaded with phosphotungstic acid (HPW@COF) has been incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to fabricate SPEEK/HPW@COF composite membranes. The one-dimensional channels of COF lined with protonated triazole (triazolium cations) by hydroscopic HPW and neutral triazole as well as counter anions (PO₄₀W₁₂³⁻) could act as proton-donors and -acceptors forming interconnected hydrogen-bonding networks, thus greatly facilitating proton conduction via Grotthuss-type mechanism particularly under low RH. Accordingly, SPEEK/HPW@COF displayed 35.5 times higher proton conductivity than the plain SPEEK at 65 °C, 40% RH. Moreover, the proton conductivity of SPEEK/HPW@COF remained constant during soaking in water for 15 days, indicating the excellent immobilization of HPW due to the electrostatic interaction between basic nitrogen sites and HPW as well as the confinement effect of microporous COF channels. These results demonstrated that N-heterocycles functionalized COFs gave great promise as effective hosts to encapsulate proton carriers.

具有高质子传导性的新型质子传导材料的设计引起了极大的兴趣。共价有机骨架（COF）是一类具有良好孔隙率和可调功能的新型多孔晶体材料，具有作为下一代质子导体的巨大潜力。在此，已将负载有磷钨酸的三唑COF（HPW @ COF）掺入磺化聚醚醚酮（SPEEK）基质中，以制造SPEEK / HPW @ COF复合膜。COF的一维通道通过吸水HPW和中性三唑以及抗衡阴离子（PO ₄₀ W ₁₂ ^3-）衬有质子化三唑（三唑阳离子））可以充当质子供体和-受体，形成相互连接的氢键网络，从而极大地促进了格罗特斯型机理的质子传导，特别是在低RH条件下。因此，在65°C，相对湿度40％的条件下，SPEEK / HPW @ COF的质子传导率是普通SPEEK的35.5倍。此外，SPEEK / HPW @ COF的质子电导率在水中浸泡15天期间保持恒定，这表明由于碱性氮位与HPW之间的静电相互作用以及微孔COF通道的限制作用，HPW具有出色的固定性。这些结果表明，N-杂环官能化的COF作为封装质子载体的有效宿主具有广阔的前景。