陕西科技大学曹丽慧团队近日研究了螺二芴基膦基离子HOFs：调节质子输运和单晶超质子电导率。2025年5月27日，《中国化学》杂志发表了这一成果。

设计具有单晶超质子导电性的离子氢键有机框架（iHOF）对于在分子水平上研究质子传导材料的机理具有重要意义。为了调节质子传输路径，研究组重点使用由不同长度脒化合物调节的立体2,2'，7,7'-四膦-9,9'-螺芴形成两个化学上相同但结构上不同的单晶iHOF-46和iHOF-47。它们都具有不同尺寸的氢键网络和高度各向异性的质子电导率，通过分析单晶结构，提出了清晰的质子传输路径。

重要的是，实验结果表明，在80°C和98%相对湿度下，具有二维（2D）氢键网络的iHOF-47在（0,0,-1）方向上的质子传导率高达0.193 S·cm^-1。单晶结构分析和密度泛函理论（DFT）计算的结合表明，iHOF-47在（0,0-1）方向上具有非常连续和平滑的质子传输路径，质子传输所需的较低能垒导致更高的质子电导率。这对于指导晶体的单向生长和建立“可见”质子传导途径具有重要意义。

附：英文原文

Title: Spirobifluorenyl Phosphonic-Based Ionic HOFs: Regulation Proton Transport and Single Crystal Superprotonic Conductivity

Author: Xiao-Jie Cao, Li-Hui Cao, Xu-Yong Chen, Simeng Qi, Bin Zhou, Xiao-Ying Hou

Issue&Volume: 2025-05-27

Abstract: The design of ionic hydrogen-bonded organic frameworks (iHOFs) with single crystal superprotonic conductivity is of great significance for studying the mechanism of proton conduction materials at molecular level. To regulate the proton transport path, this study focused on using stereoscopic 2,2',7,7'-tetraphosphone-9,9'-spirofluorene regulated by different lengths of amidine compound to form two chemically identical but structurally different single crystals iHOF-46 and iHOF-47. Both of them have hydrogen bond networks of different dimensions and highly anisotropic proton conductivity, and the clear proton transport path is proposed by analyzing the single crystal structure. Importantly, the experimental results show that iHOF-47 with a two-dimensional (2D) hydrogen bond network has a proton conductivity of up to 0.193 S·cm1 in the (0, 0, –1) direction at 80 °C and 98% RH. A combination of single-crystal structure analysis and density functional theory (DFT) calculations reveals that iHOF-47 has a very continuous and smooth proton transport path in the direction of (0, 0, –1), and the lower energy barrier required for proton transport leads to higher proton conductivity. This is significant for guiding the unidirectional growth of crystals and establishing a "visible" proton conductivity pathway.

DOI: 10.1002/cjoc.70082

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70082