Hebei Key Laboratory of Organic Functional Molecules; National Demonstration Center for Experimental Chemistry Education; College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024, Hebei, People's Republic of China.
Inorg Chem. 2022 Aug 22;61(33):13174-13183. doi: 10.1021/acs.inorgchem.2c02016. Epub 2022 Aug 9.
Exploring effective sensors for detecting possible hazards in a water system are greatly significant. This work proposed a strategy for stable and effective bifunctional sensors incorporating hourglass-type phosphomolybdates into metal-organic fragments to construct a high-dimensional framework. Two hourglass-type phosphomolybdate-based electrochemical sensors toward heavy metal ion Cr(VI) and tetracycline (TC) detection were designed with the formula [Co(HO)Na][Co(Hbpe)][Na(bpe)]{Co[PMoOH]}·9HO () and [Co(HO)Na][Co(Hbpe)][Co(bpe)]{Co[PMoOH]}·9HO () [bpe = 1,2-di(4-pyridyl)ethylene]. Structural analysis showed that hybrids and possess three-dimensional POM-supported network features with favorable stability and exhibit reversible redox properties. Experiments found that this kind of hybrids as efficient sensors have excellent electrochemical performance toward Cr(VI) detection with high sensitivities of 0.111 μA·μM for and 0.141 μA·μM for , fast response time of 1 s, and low detection limits of 30 nM for and 27 nM for , which far meet the standard of WHO for drinking water. Moreover, hybrids also exhibit fast responses to TC detection with sensitivities of 0.0073 and 0.022 μA·mM and detection limits of 0.426 and 0.084 mM. This work offers a novel strategy for the purposeful design of efficient POM-based electrochemical sensors for accurate determination of contaminants in a practical water system.
探索用于检测水体中潜在危害的有效传感器具有重要意义。本工作提出了一种策略,即将沙漏型磷钼酸盐整合到金属有机片段中,构建高维框架,以制备稳定有效的双功能传感器。通过[Co(HO)Na][Co(Hbpe)][Na(bpe)]{Co[PMoOH]}·9H_2O () 和 [Co(HO)Na][Co(Hbpe)][Co(bpe)]{Co[PMoOH]}·9H_2O () [bpe = 1,2-二(4-吡啶基)乙烯] 设计了两种基于 hourglass-type 磷钼酸盐的电化学传感器,用于检测重金属离子 Cr(VI) 和四环素 (TC)。结构分析表明,配合物 和 具有三维 POM 支撑的网络特征,具有良好的稳定性,并表现出可逆的氧化还原性质。实验发现,这种作为高效传感器的配合物对 Cr(VI) 检测具有出色的电化学性能,具有 0.111 μA·μM 的灵敏度 和 0.141 μA·μM 的灵敏度 ,快速响应时间为 1 s,检测限低至 30 nM 和 27 nM,远远超过世界卫生组织饮用水标准。此外,配合物 对 TC 检测也表现出快速响应,灵敏度分别为 0.0073 和 0.022 μA·mM,检测限分别为 0.426 和 0.084 mM。这项工作为有针对性地设计用于准确测定实际水系统中污染物的高效 POM 基电化学传感器提供了一种新策略。