高价态硼磷COFs材料理论设计与储氢性能研究

摘要/Abstract

摘要： 采用分子力学方法,从理论上设计了五种具有lta拓扑结构的高价态硼磷共价有机骨架(BP-COFs)材料。研究结果表明五种材料均具备有利于储氢应用的结构特性,如低密度(0.52~1.17 g·cm^-3)、大比表面积(1 274.12~4 033.95 m²·g^-1)和高孔隙率(0.55%~0.78%)等。使用巨正则蒙特卡罗(GCMC)方法预测298和77 K温度下五种材料对氢气分子的物理吸附性能,并分析了材料结构与氢吸附性能之间的构效关系,结果表明五种BP-COFs材料具有较强的氢气吸附能力。尤其是在77 K时,BP-COF-10和BP-COF-11在储氢性能方面的表现最为优异,BP-COF-10具有最高的体积储氢量52.86 g·L^-1,BP-COF-11具有最高的质量储氢量9.90%,而且随着压强的增加,BP-COF-11的质量储氢量仍然保持较好的上升趋势,这表明本文所设计材料具有优异的储氢应用潜力。本研究将为实验上开发新型高性能储氢材料提供一定的理论参考。

关键词: 共价有机骨架, 氢气储存, 巨正则蒙特卡罗模拟, 物理吸附, 分子力学方法

Abstract: At present, the valence state (connectivity) of most covalent organic frameworks (COFs) building units is low, mostly trivalent and tetravalent, making only 18 types of topological structures of COFs materials. On the contrary, the valence states of MOFs building blocks vary from 3 to 24, making them have more than 2 000 topological structure types. If a higher valence COFs building block can be designed, it will greatly enrich its topological structure type and material number. To this end, a hexahedral boron-phosphorus unit (-B₄P₄O₁₂-) and five linear organic linkers (phenyl, fluorophenyl, toluene, naphthalene, biphenyl) were selected, and five high-valent boron-phosphorus covalent organic frameworks (BP-COFs) with lta topology were theoretically designed by molecular mechanics methods. The results show that the five materials have structural characteristics that are conducive to hydrogen storage applications, such as low density (0.52~1.17 g·cm^-3), large specific surface area (1 274.12~4 033.95 m²·g^-1) and high porosity (0.55%~0.78%). The Grand Canonical Monte Carlo (GCMC) method was used to predict the physical adsorption properties of hydrogen molecules on five materials at 298 and 77 K, and the structure-activity relationship between material structure and hydrogen adsorption properties was analyzed. The results show that the five BP-COFs materials have strong hydrogen adsorption capacity. Especially at 77 K, BP-COF-10 and BP-COF-11 have the best performance in hydrogen storage performance. BP-COF-10 has the highest volumetric hydrogen storage capacity at 77 K, reaching 52.86 g·L^-1. BP-COF-11 has a large accessible specific surface area and high porosity. It has a good hydrogen storage capacity at 77 K and a gravimetric hydrogen storage capacity of 9.90% at 5 000 kPa. With the increase of pressure, the hydrogen storage capacity of BP-COF-11 still maintains a good upward trend. BP-COF-7 has the largest hydrogen storage capacity at 298 K, and the hydrogen storage capacity reaches 4.83 g·L^-1 at 5 000 kPa. This indicates that the designed material has good hydrogen storage potential. This study will provide a theoretical reference for the experimental development of new high-performance hydrogen storage materials.

Key words: covalent organic framework, hydrogen storage, grand canonical Monte Carlo simulation, physical adsorption, molecular mechanical method

中图分类号:

O647.32

王耀东, 李晓东, 杨朋辉, 张慧东, 刘秀英, 于景新. 高价态硼磷COFs材料理论设计与储氢性能研究[J]. 人工晶体学报, 2024, 53(4): 730-738.

WANG Yaodong, LI Xiaodong, YANG Penghui, ZHANG Huidong, LIU Xiuying, YU Jingxin. Theoretical Study on Design and Hydrogen Storage Properties of High-Valence Boron-Phosphorous Based COFs[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(4): 730-738.

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