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过程工程学报 ›› 2026, Vol. 26 ›› Issue (5): 527-538.DOI: 10.12034/j.issn.1009-606X.226111

• 研究论文 • 上一篇    下一篇

吡啶羧酸胍HOFs的氢键网络与N2O/N2吸附分离性能

贾利娜1,2， 陈诗垚2， 赵国英2*， 孙长宇1*   

  1. 1. 中国石油大学(北京)重质油国家重点实验室，北京 102249 2. 中国科学院过程工程研究所，固态电池及储能过程北京市重点实验室，介科学与过程工程全国重点实验室，北京 100190
  • 收稿日期:2026-04-17 修回日期:2026-05-11 出版日期:2026-05-28 发布日期:2026-05-28
  • 通讯作者: 赵国英 gyzhao@ipe.ac.cn
  • 基金资助:
    国家自然科学基金

Hydrogen-bonded networks and N2O/N2 adsorption separation performance of pyridinecarboxylate guanidinium HOFs

Lina JIA1,2,  Shiyao CHEN2,  Guoying ZHAO2*,  Changyu SUN1*   

  1. 1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China 2. Beijing Key Laboratory of Solid State Battery and Energy Storage Process, State Key Laboratory of Mesoscience and Process Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
  • Received:2026-04-17 Revised:2026-05-11 Online:2026-05-28 Published:2026-05-28
  • Contact: ZHAO Guo-ying gyzhao@ipe.ac.cn

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摘要： 高效捕获温室气体一氧化二氮(N2O)对缓解温室效应、实现资源回收具有重要意义。本工作以2,2'-联吡啶-5,5'-二羧酸和2,2'-联吡啶-4,4'-二羧酸为配体，成功构筑了两种吡啶氮位点异构的胍基氢键有机框架(HOFs)——2,2'-联吡啶-5,5'-二羧酸胍(G-5,5'-BPyDC)和2,2'-联吡啶-4,4'-二羧酸胍(G-4,4'-BPyDC)。通过单晶X射线衍射、热重分析、Hirshfeld表面分析及气体吸附实验，系统研究了配体结构异构对氢键网络、孔道环境及N2O/N2吸附分离性能的影响。结果表明，两种HOFs均通过N-H…O氢键构筑三维框架结构：G-5,5'-BPyDC的不对称单元含两个甲醇分子，其自由体积和表面积大于G-4,4'-BPyDC，而后者分子堆积更为紧密；两种材料的起始分解温度均≥290℃，表现出良好的热稳定性。Hirshfeld表面分析显示，G-5,5'-BPyDC中O-H/H-O与N-H/H-N氢键总贡献(32.0%)高于G-4,4'-BPyDC (29.7%)。气体吸附测试表明，在25℃, 4.0 MPa条件下，G-5,5'-BPyDC对N2O的吸附容量为2.32 mmol/g，高于G-4,4'-BpyDC (2.02 mmol/g)。IAST计算结果显示，G-5,5'-BPyDC对N2O/N2 (50∶50和10∶90)混合气的选择性分别达29.26和111.32，显著优于G-4,4'-BPyDC (6.61和17.03)。综上，吡啶氮位点异构可通过调控框架孔道极性及氢键网络，有效优化N2O/N2吸附分离性能，该研究为异构体设计策略提供了新思路。

关键词: 氢键有机框架, 胍基材料, 吡啶氮位点异构, N2O/N2吸附分离

Abstract: Efficient capture of the greenhouse gas nitrous oxide (N2O) is of great significance for mitigating climate change and resource recovery. In this study, two guanidinium-based hydrogen-bonded organic frameworks (HOFs) with pyridyl nitrogen site isomerism, namely G-5,5'-BPyDC and G-4,4'-BPyDC, were successfully constructed using 2,2'-bipyridine-5,5'-dicarboxylic acid and 2,2'-bipyridine-4,4'-dicarboxylic acid as ligands. The effects of ligand structure on the hydrogen-bonded network, pore environment, and N2O/N2 adsorption and separation performance were systematically investigated by single-crystal X-ray diffraction, thermogravimetric analysis, Hirshfeld surface analysis, and gas adsorption experiments. The results showed that both frameworks were constructed via N-H…O hydrogen bonds. However, the asymmetric unit of G-5,5'-BPyDC contained two methanol molecule, and its free volume and surface area were larger than those of G-4,4'-BPyDC, while the latter exhibited a more compact molecular packing. Both materials exhibited an decomposition temperature above 290℃, showing good thermal stability. Hirshfeld surface analysis revealed that the total contribution of O-H/H-O and N-H/H-N hydrogen bonds in G-5,5'-BPyDC (32.0%) was higher than that in G-4,4'-BPyDC (29.7%). At 25℃ and 4.0 MPa, the N2O adsorption capacity of G-5,5'-BPyDC was 2.32 mmol/g, higher than that of G-4,4'-BPyDC (2.02 mmol/g). IAST calculations indicate that the selectivities of G-5,5'-BPyDC for N2O/N2 (50∶50 and 10∶90) mixtures reached 29.26 and 111.32, respectively, significantly superior to those of G-4,4'-BPyDC (6.61 and 17.03). In conclusion, pyridyl nitrogen site isomerism can effectively optimize N2O/N2 adsorption and separation performance by modulating the pore polarity and hydrogen-bonded network of the frameworks, providing a new strategy for isomer design.

Key words: hydrogen-bonded organic frameworks, guanidinium-based materials, pyridinic nitrogen site isomerism, N2O/N2 adsorption separation