School of Ocean Information Engineering, Jimei University, Xiamen, 361021, China.
School of Ocean Information Engineering, Jimei University, Xiamen, 361021, China.
Chemosphere. 2022 Sep;302:134785. doi: 10.1016/j.chemosphere.2022.134785. Epub 2022 Apr 30.
In this work, we reported a modified COF material for trinitrophenol (TPA) ratiometric sensing and removal. Here a cationic covalent organic framework (C-COF) was prepared as host, while two Tb(III)-based ions were doped into C-COF as probe by ionic exchange reaction with probe loading level of ∼15%. In the absence of TPA, weak Tb(III) emission (489 nm, 545 nm, 585 nm) and bright red COF emission were observed (633 nm). The addition of TPA increased Tb(III) emission and decreased COF emission, following linear response within TPA concentration region of 0-9 μM. Their limit of detection values were determined as 0.9 μM and 4.5 μM, respectively. Corresponding working equations were fitted as I/I = 1.225 + 6.914 × 10 M[TPA], R = 0.997 for TbCF-COF and I/I = 1.063 + 9.222 × 10 M [TPA], R = 0.993 for TbDBM-COF. TbCF-COF showed better sensing performance than TbDBM-COF, due to its suitable ligand triplet energy level. Their sensing mechanism was revealed as dopant "replacement", where dopant molecules loaded in COF micropore were replaced by TPA molecules, accompanied with energy competing on Tb(III) D level, showing ratiometric signals. Good selectivity and removal capacity (∼7.4 wt%) for TPA were achieved.
在这项工作中，我们报道了一种用于三硝基苯酚（TPA）比率传感和去除的改性 COF 材料。在这里，制备了一种阳离子共价有机框架（C-COF）作为主体，而通过离子交换反应将两个基于 Tb(III)的离子掺杂到 C-COF 中作为探针，探针负载水平约为 15%。在没有 TPA 的情况下，观察到弱的 Tb(III)发射（489nm、545nm、585nm）和明亮的红色 COF 发射（633nm）。添加 TPA 增加了 Tb(III)的发射并降低了 COF 的发射，在 TPA 浓度为 0-9μM 的范围内呈线性响应。它们的检测限分别确定为 0.9μM 和 4.5μM。相应的工作方程拟合为 I/I=1.225+6.914×10M[TPA]，R=0.997（用于 TbCF-COF）和 I/I=1.063+9.222×10M[TPA]，R=0.993（用于 TbDBM-COF）。由于其合适的配体三重态能级，TbCF-COF 比 TbDBM-COF 具有更好的传感性能。它们的传感机制被揭示为掺杂剂“取代”，其中 COF 微孔中负载的掺杂分子被 TPA 分子取代，同时在 Tb(III)D 能级上发生能量竞争，显示出比率信号。实现了对 TPA 的良好选择性和去除能力（约 7.4wt%）。
