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[1]韩 冰,梁 恩,张 诣,等.新型富氮多孔有机材料的合成及催化性能研究[J].武汉工程大学学报,2025,47(03):267-273.[doi:10.19843/j.cnki.CN42-1799/TQ.202502005]
　HAN Bing,LIANG En,ZHANG Yi,et al.Synthesis of a novel nitrogen-rich porous organic polymer and its catalytic performance[J].Journal of Wuhan Institute of Technology,2025,47(03):267-273.[doi:10.19843/j.cnki.CN42-1799/TQ.202502005]
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新型富氮多孔有机材料的合成及催化性能研究
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《武汉工程大学学报》[ISSN:1674-2869/CN:42-1779/TQ]

卷:
47
期数:
2025年03期
页码:
267-273
栏目:
现代大化工
出版日期:
2025-06-30

文章信息/Info

Title:
Synthesis of a novel nitrogen-rich porous organic polymer and its catalytic performance
文章编号:
1674 - 2869（2025）03 - 0267 - 07
作者:
1.武汉工程大学化工与制药学院，湖北 武汉 430205;
2.武汉工程大学化学与环境工程学院，湖北 武汉 430205
Author(s):
1. School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China；
2. School of Chemistry and Environmental Engineering，Wuhan Institute of Technology，Wuhan 430205，China
关键词:
Keywords:
分类号:
O643.36
DOI:
10.19843/j.cnki.CN42-1799/TQ.202502005
文献标志码:
A
摘要:
多孔有机材料（POPs）凭借其低骨架密度、高比表面积、可调孔径、易功能化及优异稳定性等特点，在气体吸附、分离及非均相催化领域展现出重要应用潜力。通过"自下而上"的分子设计策略，将富氮嘧啶杂环结构单元精准引入POPs骨架，成功制备了新型氮掺杂多孔材料TMB-TPAD-POP。采用X射线衍射（XRD）、扫描电子显微镜（SEM）、热重分析（TG）和氮气吸附-脱附等温线等技术系统表征了材料的晶体结构、微观形貌、热稳定性及孔隙特性。以苯甲醛与丙二腈的Knoevenagel缩合为模型反应，在80 ℃条件下，TMB-TPAD-POP展现出显著催化性能，8 h内产率达99%。机理研究表明：联嘧啶环中相邻氮原子协同活化底物：其孤对电子可活化丙二腈的α-C，促进碳负离子的高效形成，并通过稳定反应中间态显著降低活化能，从而实现产率的显著提升。本研究为构建高效氮杂环催化体系提供了新的设计思路，拓展了功能化POPs在有机合成中的应用。
Abstract:
Porous organic polymers (POPs) have emerged as promising materials for gas adsorption, separation, and heterogeneous catalysis, owing to their low skeletal density, high specific surface area, tunable pore size, facile functionalization, and exceptional stability. In this study, a novel nitrogen-doped porous material, TMB-TPAD-POP, was successfully synthesized through a "bottom-up" molecular design strategy that precisely incorporated nitrogen-rich pyrimidine heterocyclic units into the POP framework.?The material was systematically characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG), and nitrogen adsorption-desorption isotherms to elucidate its crystal structure, micromorphology, thermal stability, and porosity. When employed as a catalyst for the Knoevenagel condensation of benzaldehyde and malononitrile under solvent-free conditions at 80 ℃, TMB-TPAD-POP demonstrated outstanding catalytic performance, achieving a 99% yield within 8 hours. Mechanistic studies revealed that adjacent nitrogen atoms in the bipyrimidine rings synergistically activate substrates: their lone-pair electrons facilitate the activation of the a-C in malononitrile, enabling efficient formation of carbon nucleophiles, while simultaneously stabilizing reaction intermediates to significantly reduce the activation energy, thereby enhancing the reaction yield. This study provides a new design strategy for constructing high-performance nitrogen-rich catalytic systems and expands the application of functionalized POPs in organic synthesis.

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备注/Memo

备注/Memo:
收稿日期：2025-02-18
基金项目：国家自然科学基金（51203127）
作者简介：韩 冰，硕士研究生。Email：1575605905@qq.com
*通信作者：余响林，博士，教授。Email：yxlin2002@163.com
引文格式：韩冰，梁恩，张诣，等. 新型富氮多孔有机材料的合成及催化性能研究［J］. 武汉工程大学学报，2025，47（3）：267-273.
更新日期/Last Update: 2025-07-08