Mechanistic study of TPE-Ph COF for fluorescent ammonia detection  

TPE-Ph COF荧光检测氨的机理研究

作　　者：LUO Na LI Hongjiang CUI Yingna HAO Ce LI Shenmin 罗娜;李泓江;崔颖娜;郝策;李慎敏(大连大学环境与化学工程学院,辽宁大连116622;大连理工大学化工学院,辽宁大连116024)

机构地区：[1]School of Environmental and Chemical Engineering,Dalian University,Dalian 116622,China [2]School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China

出　　处：《分子科学学报》2024年第4期363-370,共8页Journal of Molecular Science

摘　　要：In this study,the interaction between TPE-Ph COF and ammonia molecules,as well as the mechanism of fluorescence detection of ammonia,were comprehensively investigated using density functional theory(DFT)and time-dependent density functional theory(TD-DFT).It was found that the binding between TPE-Ph COF and ammonia molecules occurs primarily through coordination bonds or hydrogen bonds.Specifically,the formation of coordination bonds significantly changes the intramolecular charge transfer of TPE-Ph COF,leading to fluorescence quenching.Computational analysis revealed the changes in electron and hole distributions upon the binding of ammonia to TPE-Ph COF,as well as the competition between nonradiative and radiative transitions during the photophysical processes,thereby elucidating the intrinsic mechanism of fluorescence response.采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)深入探究了TPE-Ph COF与氨分子的相互作用及其荧光检测氨气的机理。研究发现,TPE-Ph COF与氨分子的结合主要通过配位键或氢键2种方式,其中配位键的形成显著改变了TPE-Ph COF分子内的电荷转移,导致荧光淬灭现象。通过分析,揭示了氨与TPE-Ph COF结合后的电子与空穴分布变化,以及光物理阶段的非辐射跃迁与辐射跃迁之间竞争关系,从而明确了荧光响应的内在机制。

关 键 词：time-dependent density functional theory(TD-DFT) luminescent covalent organic frameworks charge transfer fluorescence sensing detection 

分 类 号：O657.3[理学—分析化学]