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基于金属有机框架结合硫量子点的荧光传感器超灵敏检测水环境中的 Cr(VI)(CrO/CrO)离子。

Ultrasensitive detection of Cr(VI) (CrO/CrO) ions in water environment with a fluorescent sensor based on metal-organic frameworks combined with sulfur quantum dots.

机构信息

State Key Laboratory of Pollution Control and Resource Reuse, International Joint Research Center for Sustainable Urban Water System, College of Environmental Science & Engineering, Tongji University, 1239 Siping Road, Shanghai, 200092, PR China.

State Key Laboratory of ASIC and System, School of Microelectronics, Fudan University, Shanghai, 200433, PR China.

出版信息

Anal Chim Acta. 2020 Sep 22;1131:68-79. doi: 10.1016/j.aca.2020.07.026. Epub 2020 Jul 30.

Abstract

Accurate, simple and quick detection methods for Cr(VI) detection are urgently needed for water quality monitoring. Herein, a novel and facile method of detecting Cr(VI) (CrO/CrO) ions is developed via the fluorescent detection technology based on metal-organic frameworks (MOFs) doped with sulfur quantum dots (SQDs) (SQDs@UiO-66-NH). The blue-light-emitting SQDs@UiO-66-NH composites exhibit excellent fluorescent properties in water environment with high quantum yield (68%) and ideal fluorescent stability, thus demonstrating excellent potential for serving as a chemical sensor. After characterizing the performance and stability of SQDs@UiO-66-NH, qualitative and quantitative detection of CrO and CrO ions was successfully conducted. The fluorescence of SQDs@UiO-66-NH composites in aqueous solution was quenched effectively with more than 90% quenching efficiency by Cr(VI) via the inner filter effect. The detection system provides considerable advantages such as rapid response (10 s), high sensitivity with a low detection limit of 0.16 μM in a broad linear range of 0-200 μM (R = 0.99) for CrO and 0.17 μM for CrO in a broad linear range of 0-220 μM (R = 0.99), high selectivity and reproducibility for at least five cycles with simple washing with alcohol. In practical applications, the sensor showed rapid response, high sensitivity and excellent recoveries (96.7%-105.4%) for detecting CrO in real water samples. Furthermore, a SQDs@UiO-66-NH-based fluorescent test paper was successfully developed, providing a simple, reliable and portable method for Cr(VI) (CrO/CrO) detection in water environment.

摘要

用于水质监测的准确、简单、快速的 Cr(VI)检测方法亟待开发。在此,我们通过基于金属有机骨架(MOFs)掺杂硫量子点(SQDs)的荧光检测技术,开发了一种新颖且简便的检测 Cr(VI)(CrO₄²⁻/Cr₂O₇²⁻)离子的方法(SQDs@UiO-66-NH)。发现在水环境中,具有高量子产率(68%)和理想荧光稳定性的蓝光发射 SQDs@UiO-66-NH 复合材料具有优异的荧光性能,因此具有作为化学传感器的优异潜力。在对 SQDs@UiO-66-NH 的性能和稳定性进行了表征后,成功地对 CrO₄²⁻和 Cr₂O₇²⁻离子进行了定性和定量检测。Cr(VI)通过内滤效应有效猝灭了 SQDs@UiO-66-NH 复合材料在水溶液中的荧光,猝灭效率超过 90%。该检测系统具有快速响应(10 s)、高灵敏度(CrO₄²⁻的检测限低至 0.16 μM,线性范围为 0-200 μM,R²=0.99;Cr₂O₇²⁻的检测限低至 0.17 μM,线性范围为 0-220 μM,R²=0.99)、高选择性和重现性等优点,且经过简单的酒精清洗后至少可以重复使用五次。在实际应用中,该传感器对实际水样中 CrO₄²⁻的检测表现出快速响应、高灵敏度和良好的回收率(96.7%-105.4%)。此外,成功制备了基于 SQDs@UiO-66-NH 的荧光测试纸条,为水环境中 Cr(VI)(CrO₄²⁻/Cr₂O₇²⁻)的检测提供了一种简单、可靠和便携的方法。

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