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Ligand-variable metal clusters charge transfer in Ce-Por-MOF/AgNWs and their application in photoelectrochemical sensing of ronidazole

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Abstract

A photoelectrochemical sensing platform based on ligand-variable metal clusters charge transfer was established for the quantitative assay of ronidazole (RNZ) using Ce-porphyrin-metal–organic frameworks/silver nanowires (Ce-Por-MOFs/AgNWs). Rod-like Ce-Por-MOFs and well-dispersed sub-50 nm AgNWs were prepared using a hydrothermal method and polyol strategy, and then through simple drop coating to yield Ce-Por-MOFs/AgNWs nanocomposites. We investigated the intrinsic semiconducting properties of the composites. More importantly, it was found that the variable-valence metal node can provide electronic defect states similar to those caused by multi-metal doping, synergizing with the surface plasmon effect of AgNWs, which significantly improved the photoelectric conversion efficiency, thereby resulting in excellent optoelectronic properties. In combination with molecular imprinting, a competitive type trace photoelectrochemical sensor for RNZ was constructed using Fe2+ as the electron donor and probe. Under optimal conditions, the sensor response is proportional to the logarithm of RNZ concentration in the range 0.1–104 nM with a detected limit of 0.038 nM. The recoveries ranged from 87.2 to 116% with relative standard deviations (RSDs) < 6.5% (n = 3) in milk sample. This work reveals the charge-transfer process of variable-valence metal nodes in MOFs during photoelectrochemical processes, which will provide new insights for the sensing application of variable-valence metal MOFs.

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Funding

This work was supported by Central Public-interest Scientific Institution Basal Research Fund for Chinese Academy of Tropical Agricultural Sciences (No. 1630082021005, 1630082022008), China Agriculture Research System of MOF and MARA (CARS-31). Key Laboratory of Tropical Fruits and Vegetables Quality and Safety for State Market Regulation (Grant No. ZX-2022002), the National Natural Science Foundation of China (No. 21964008), and the Natural Science Foundation of Guangxi Province (No. 2020GXNSFBA159050 and 2019GXNSFBA245100).

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Authors and Affiliations

  1. Guangxi Key Laboratory of Electrochemical and Magnetochemical Function Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, 541004, China

    Jinsheng Kang & Jianping Li

  2. Analysis and Test Center, Hainan Provincial Key Laboratory of Quality and Safety for Tropical Fruits and Vegetables, Key Laboratory of Quality and Safety Control for Subtropical Fruit and Vegetable, Ministry of Agriculture and Rural Affairs Haikou, Chinese Academy of Tropical Agricultural Sciences, Haikou, 571101, China

    Xionghui Ma, Yuwei Wu, Chaohai Pang, Shuhuai Li, Jinhui Luo, Mingyue Wang & Zhi Xu

  3. Key Laboratory of Tropical Fruits and Vegetables Quality and Safety for State Market Regulation, Haikou, 570311, China

    Xionghui Ma, Yuwei Wu, Chaohai Pang, Shuhuai Li, Jinhui Luo, Mingyue Wang & Zhi Xu

  4. College of Food and Bioengineering, Hezhou University, Hezhou, 542899, China

    Yuhao Xiong

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  1. Jinsheng Kang
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Kang, J., Ma, X., Wu, Y. et al. Ligand-variable metal clusters charge transfer in Ce-Por-MOF/AgNWs and their application in photoelectrochemical sensing of ronidazole. Microchim Acta 189, 383 (2022). https://doi.org/10.1007/s00604-022-05477-1

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