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<p>The development of highly sensitive photo-assisted electrochemical (PAEC) sensors for trace detection of heavy metal ions (such as chromium (VI) [Cr(VI)]) is crucial. Herein, three isomorphic compounds, namely {[M(H<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>[M(HTetp)(H<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>[M(P<sub>4</sub>Mo<sub>6</sub>O<sub>31</sub>H<sub>6</sub>)<sub>2</sub>]}·nH<sub>2</sub>O (M = Ni/Co/Fe, n = 5 for <b>Ni-P</b><sub><b>4</b></sub><b>Mo</b><sub><b>6</b></sub>, n = 1 for <b>Co-P</b><sub><b>4</b></sub><b>Mo</b><sub><b>6</b></sub> and <b>Fe-P</b><sub><b>4</b></sub><b>Mo</b><sub><b>6</b></sub>, Tetp = 4-[4-(2-Thiophen-2-yl-ethyl)-4H-[1,2,4]triazole-3-yl]-pyridine) are synthesized and directly used as electrode materials for PAEC sensors to detect Cr(VI). The excellent photo-electrochemical properties of the M{P<sub>4</sub>Mo<sub>6</sub>} based compounds originate from two key factors: (1) the synergistic combination of polyoxometalates (POMs) clusters and transition metal–organic components (TMCs), which promotes interfacial charge transfer. (2) the unique hourglass-shaped structure of the M{P<sub>4</sub>Mo<sub>6</sub>} clusters, providing abundant active sites for Cr(VI) adsorption and reduction. In particular, <b>Ni-P</b><sub><b>4</b></sub><b>Mo</b><sub><b>6</b></sub> exhibits a high sensitivity of 584.81 μA·μM<sup>−1</sup> and an ultra-low LOD of 2.34 nM under 40&#xa0;W white light, surpassing most reported Cr(VI) sensors. The&#xa0;detection of Cr(VI) in real water samples highlights the&#xa0;potential of the sensor&#xa0;in environmental monitoring.</p> Graphical abstract <p></p>

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Hourglass-type M{P4Mo6}2 as photo-assisted electrochemical sensors for ultrasensitive detection of trace-level Cr(VI)

  • 期刊论文

  • 发表日期：

    2025年6月3日

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  • Kaili Hui,
  • Tao Liu,
  • Mengle Yang,
  • Aixiang Tian,
  • Jun Ying,
  • Xixian Cao

摘要

The development of highly sensitive photo-assisted electrochemical (PAEC) sensors for trace detection of heavy metal ions (such as chromium (VI) [Cr(VI)]) is crucial. Herein, three isomorphic compounds, namely {[M(H2O)2]2[M(HTetp)(H2O)2]2[M(P4Mo6O31H6)2]}·nH2O (M = Ni/Co/Fe, n = 5 for Ni-P4Mo6, n = 1 for Co-P4Mo6 and Fe-P4Mo6, Tetp = 4-[4-(2-Thiophen-2-yl-ethyl)-4H-[1,2,4]triazole-3-yl]-pyridine) are synthesized and directly used as electrode materials for PAEC sensors to detect Cr(VI). The excellent photo-electrochemical properties of the M{P4Mo6} based compounds originate from two key factors: (1) the synergistic combination of polyoxometalates (POMs) clusters and transition metal–organic components (TMCs), which promotes interfacial charge transfer. (2) the unique hourglass-shaped structure of the M{P4Mo6} clusters, providing abundant active sites for Cr(VI) adsorption and reduction. In particular, Ni-P4Mo6 exhibits a high sensitivity of 584.81 μA·μM−1 and an ultra-low LOD of 2.34 nM under 40 W white light, surpassing most reported Cr(VI) sensors. The detection of Cr(VI) in real water samples highlights the potential of the sensor in environmental monitoring.

Graphical abstract