Solid-State Fluorescent Organic Polymers for Visual Detection and Elimination of Heavy Metals in Water

Debashis Barik, Abhirami Anilkumar and Mintu Porel*, 
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Abstract

Selective sensing and removal of toxic heavy metals from water are highly essential since their presence poses significant health and environmental hazards. Herein, we designed and synthesized a novel fluorescent nonconjugated organic polymer by strategically incorporating two key functional groups, namely, a dansyl fluorophore and dithiocarbamate (DTC). Different characterization techniques, including 1H nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR), and fluorescence spectroscopy, were performed to understand its structure and material properties. The quantum yield of 4.72% and its solid-state fluorescence indicate that it has potential for various applications in several technological and scientific domains. In this study, we investigated a specific application involving the detection and elimination of heavy metals from water. Interestingly, the presence of dansyl and DTC moieties demonstrated remarkable selectivity toward Cu2+, Co2+, Ni2+, Fe3+, and Fe2+ sensing, displaying distinct color changes specific to each metal. Cu2+ resulted in a yellow color, Co2+ showed a green color, Ni2+ displayed a pale yellowish-green color, and Fe2+/Fe3+ exhibited a brown color. The LOD (limit of detection) for each metal was obtained in the nanomolar range by using a fluorescence spectrometer and the micromolar range from UV–visible spectra: 13.27 nM and 0.518 μM for Cu2+, 8.27 nM and 0.581 μM for Co2+, 14.36 nM and 0.140 μM for Ni2+, 14.95 nM and 0.174 μM for Fe2+, and 15.54 nM and 0.33 μM for Fe3+. Moreover, the DTC functionality on its backbone facilitates effective interaction with the aforementioned heavy metals, subsequently removing them from water (except Fe2+ and Fe3+), validating its dual functionality as both an indicator and a purifier for heavy metals in water. The polymer exhibited a maximum adsorption capacity of 192.30 mg/g for Cu2+, 159.74 mg/g for Co2+, and 181.81 mg/g for Ni2+. Furthermore, this approach exhibits versatility in crafting fluorescent polymers with adjustable attributes that are suitable for a wide range of applications.

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用于目测和消除水中重金属的固态荧光有机聚合物
选择性地感知和去除水中的有毒重金属非常重要,因为重金属的存在会对健康和环境造成严重危害。在本文中,我们设计并合成了一种新型的荧光非共轭有机聚合物,策略性地加入了两个关键官能团,即丹尼斯荧光团和二硫代氨基甲酸乙酯(DTC)。研究人员采用了不同的表征技术,包括 1H 核磁共振 (NMR)、扫描电子显微镜 (SEM)、X 射线衍射 (XRD)、能量色散 X 射线分析 (EDAX)、傅立叶变换红外光谱 (FTIR) 和荧光光谱,以了解其结构和材料特性。4.72% 的量子产率及其固态荧光表明,它具有在多个技术和科学领域进行各种应用的潜力。在这项研究中,我们调查了涉及检测和消除水中重金属的具体应用。有趣的是,丹酰和 DTC 分子的存在显示了对 Cu2+、Co2+、Ni2+、Fe3+ 和 Fe2+ 的显著选择性,并显示出每种金属特有的颜色变化。Cu2+ 呈黄色,Co2+ 呈绿色,Ni2+ 呈淡黄绿色,Fe2+/Fe3+ 呈棕色。利用荧光光谱仪和紫外可见光谱获得了每种金属的纳摩尔检测限(LOD)和微摩尔检测限(LOD):Cu2+ 为 13.27 nM 和 0.518 μM,Co2+ 为 8.27 nM 和 0.581 μM,Ni2+ 为 14.36 nM 和 0.140 μM,Fe2+ 为 14.95 nM 和 0.174 μM,Fe3+ 为 15.54 nM 和 0.33 μM。此外,其主干上的 DTC 功能还能促进与上述重金属的有效相互作用,随后将它们从水中去除(Fe2+ 和 Fe3+ 除外),从而验证了其作为水中重金属指示剂和净化剂的双重功能。该聚合物对 Cu2+、Co2+ 和 Ni2+ 的最大吸附容量分别为 192.30 毫克/克、159.74 毫克/克和 181.81 毫克/克。此外,这种方法在制作具有可调属性的荧光聚合物方面具有多功能性,适合广泛的应用。
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