Yang Feng-Fan, Wang Xiao-Lu, Tian Jiayue, Yin Yang, Liang Linfeng
Institute of Crystalline Materials, Shanxi University, Taiyuan, 030006, Shanxi, China.
College of Chemistry, Taiyuan University of Technology, Taiyuan, 030024, China.
Nat Commun. 2024 May 10;15(1):3930. doi: 10.1038/s41467-024-48158-8.
Hydrogen-bonded organic frameworks (HOFs) are versatile materials with potential applications in proton conduction. Traditional approaches involve incorporating humidity control to address grain boundary challenges for proton conduction. This study finds vitrification as an alternative strategy to eliminate grain boundary effect in HOFs by rapidly melt quenching the kinetically stable HOF-SXU-8 to glassy state HOF-g. Notably, a remarkable enhancement in proton conductivity without humidity was achieved after vitrification, from 1.31 × 10S cm to 5.62× 10S cm at 100 °C. Long term stability test showed negligible performance degradation, and even at 30 °C, the proton conductivity remained at high level of 1.2 × 10S cm. Molecule dynamics (MD) simulations and X-ray total scattering experiments reveal the HOF-g system is consisted of three kinds of clusters, i.e., 1,5-Naphthalenedisulfonic acid (1,5-NSA) anion clusters, N,N-dimethylformamide (DMF) molecule clusters, and H-HO clusters. In which, the H plays an important role to bridge these clusters and the high conductivity is mainly related to the H on HO. These findings provide valuable insights for optimizing HOFs, enabling efficient proton conduction, and advancing energy conversion and storage devices.
氢键有机框架（HOFs）是具有质子传导潜在应用的多功能材料。传统方法涉及引入湿度控制以解决质子传导中的晶界挑战。本研究发现玻璃化是一种替代策略，通过将动力学稳定的HOF-SXU-8快速熔融淬火至玻璃态HOF-g来消除HOFs中的晶界效应。值得注意的是，玻璃化后在无湿度条件下质子传导率显著提高，在100°C时从1.31×10S cm提高到5.62×10S cm。长期稳定性测试表明性能降解可忽略不计，甚至在30°C时，质子传导率仍保持在1.2×10S cm的高水平。分子动力学（MD）模拟和X射线全散射实验表明HOF-g系统由三种簇组成，即1,5-萘二磺酸（1,5-NSA）阴离子簇、N,N-二甲基甲酰胺（DMF）分子簇和H-HO簇。其中，H在连接这些簇中起重要作用，高传导率主要与HO上的H有关。这些发现为优化HOFs、实现高效质子传导以及推进能量转换和存储设备提供了有价值的见解。
