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Functional decoration on a regenerable bifunctional porous covalent organic framework probe for rapid detection and adsorption of copper ions

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Abstract

Developing fluorescence porous probe for detecting and eliminating Cu2+ contamination in water or biosystem is an essential research project that has attracted considerable attention. However, improving the fluorescence detecting efficiency while enhancing the adsorption capacity of the porous probe is of great challenge. Herein, a bifunctional two-dimensional imine-based porous covalent organic framework (TTP-COF) probe was designed and synthesized from 1,3,5-tris (4-aminophenyl) benzene (TAPB) and 2,4,6-Triformylphloroglucinol (TP) ligand. TTP-COF displayed rapid detection of Cu2+ (limit of detection (LOD) = 10 nmol·L−1 while achieving a high adsorption capacity of 214 mg·g−1 (pH = 6) at room temperature with high reusability (> 5 cycles). The key roles and contributions of high π-conjugate and delocalized electrons in TABP and functional –OH groups in TP were proved. More importantly, the fluorescence quenching mechanism of TTP-COF was studied by density functional theory theoretical calculations, revealing the crucial role of intramolecular hydrogen bonds among C=N and –OH groups and the blocking of the excited state intramolecular proton transfer process in detecting process of Cu2+.

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摘要

开发用于检测和消除水中或生物系统中Cu2+污染的荧光多孔探针是一项备受关注的重要工作。然而，在提高多孔探针的吸附能力的同时提高荧光检测效率是一项巨大的挑战。在本文中，以1，3，5-三（4-氨基苯基）苯（TAPB）和2，4，6-三甲酰基间苯三酚（TP）为原料，设计合成了一种双功能二维亚胺基多孔共价有机框架探针（TTP-COF）。该探针显示出对Cu2+的快速检测能力（LOD=10 nmol·L−1），高的吸附容量（214 mg·g-1，pH=6）且具有多次循环使用性能（＞5个循环）。TABP中高π共轭电子和离域电子以及TP中功能-OH基团的关键作用和贡献导致探针具有强荧光。更重要的是，通过DFT理论计算研究了TTP-COF的荧光淬灭机制，揭示了C=N和-OH基团之间的分子内氢键存在的重要性以及在Cu2+检测过程中激发态分子内质子转移（ESIPT）过程的阻断作用导致荧光发生变化。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 22001156 and 22271178), the Innovation Capability Support Program of Shaanxi (No. 2022KJXX-88) and the Technology Innovation Leading Program of Shaanxi (No. 2020QFY07-05).

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Authors and Affiliations

  1. School of Materials and Chemical Engineering, Xi’an Technological University, Xi’an, 710021, China

    Yu-Long Li, Xi-Lang Jin, Yi-Ting Ma, Jing-Rui Liu, Hong-Wei Zhou & Wei-Xing Chen

  2. Key Laboratory of Chemical Additives for China National Light Industry, College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi’an, 710021, China

    Peng-Yuan Zhu & Wen-Huan Huang

  3. KAUST Catalysis Center, King Abdullah University of Science and Technology, 23955-6900, Thuwal, Kingdom of Saudi Arabia

    Fazal Raziq

  4. Yulin Boyi-Jingking Research Institute of Industrial Technology Development Research, Yulin, 719054, China

    Xi-Lang Jin

  5. National and Local Joint Engineering Laboratory for Slag Comprehensive Utilization and Environmental Technology, School of Materials Science and Engineering, Shaanxi University of Technology, Hanzhong, 723001, China

    Zhi-Feng Deng

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Li, YL., Jin, XL., Ma, YT. et al. Functional decoration on a regenerable bifunctional porous covalent organic framework probe for rapid detection and adsorption of copper ions. Rare Met. 43, 758–769 (2024). https://doi.org/10.1007/s12598-023-02476-w

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