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Metal-organic framework film for fluorescence turn-on H2S gas sensing and anti-counterfeiting patterns

基于金属有机框架薄膜材料的硫化氢气体荧光增强型探针和图案防伪

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Abstract

Hydrogen sulphide (H2S) is a common air pollutant, which is produced in various industry processes. Therefore, it is of crucial importance to detect H2S in real time. Many fluorescent sensors were reported aiming at detecting H2S in solution; however, the fluorescence sensing of gaseous H2S has not yet been reported. In this work, we utilized the post-functionalized fluorescent film, MIL-100(In)@Eu3+/Cu2+ film, realizing fluorescence turn-on sensing of gaseous H2S at room temperature for the first time with the limit of detection as low as 0.535 ppm, which is comparable to some reported fluorescent probes for S2− ions and semiconductor based gaseous H2S sensors. The sensor was designed due to the strong affinity of H2S with Cu2+. With the formation of CuS, the “antenna effect” between the ligand and Eu3+ recovered, resulting in the fluorescence turn-on of Eu3+ emission. Additionally, we proposed a new method to realize multi-colour anti-counterfeiting patterns with lanthanide ions ink, taking advantage of the extraordinary smooth surface and uncoordinated carboxylate groups within the MIL-100(In) film.

摘要

硫化氢气体是一种常见的工业气体, 也是一种大气污染物, 因此对硫化氢气体的实时检测具有十分重要的意义. 当前报道的硫化氢荧光探针大多是在溶液中进行探测的, 能检测硫化氢气体的荧光探针还鲜有报道. 本文利用后修饰的具有荧光发光潜力的薄膜, MIL-100(In)@Eu3+/Cu2+, 在室温下首次实现了对硫化氢气体的荧光增强型检测, 检测限可达0.535 ppm. 此探针的设计是基于硫化氢气体与Cu2+的强结合力. 当形成CuS之后, 有机配体与Eu3+之间的“天线效应”恢复, 使得Eu3+的荧光发射增强. 这个荧光探针的性能可以与溶液中检测硫化氢的荧光探针相媲美, 并且不输于传统的半导体型硫化氢气体探针. 此外, 由于MIL-100(In)薄膜表面平 整度高且具有未配位的羧基基团, 我们利用稀土离子溶液在其表面上实现了多色防伪图案.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (U1609219, 51632008, 61721005, 51432001 and 51772268), and Zhejiang Provincial Natural Science Foundation (LD18E020001).

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Authors and Affiliations

  1. State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials and Applications, School of Material Science and Engineering, Zhejiang University, Hangzhou, 310027, China

    Jun Zhang  (张骏), Yuanjing Cui  (崔元靖), Bin Li  (李斌), Yu Yang  (杨雨) & Guodong Qian  (钱国栋)

  2. College of Electrical Engineering, Zhejiang University, Hangzhou, 310027, China

    Fang Liu  (刘芳)

  3. State Key Laboratory of Luminescent Materials and Devices and Institute of Optical Communication Materials, South China University of Technology, Guangzhou, 510640, China

    Jiulin Gan  (甘久林)

Authors
  1. Jun Zhang  (张骏)
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  2. Fang Liu  (刘芳)
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  3. Jiulin Gan  (甘久林)
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  4. Yuanjing Cui  (崔元靖)
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  5. Bin Li  (李斌)
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  6. Yu Yang  (杨雨)
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  7. Guodong Qian  (钱国栋)
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Contributions

Author contributions Zhang J designed and performed the experiments, analyzed the data and wrote the paper; Liu F designed partial experiments. Gan J, Yang Y and Li B analyzed the data; Cui Y and Qian G conceived the framework of this paper and revised the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yuanjing Cui  (崔元靖) or Guodong Qian  (钱国栋).

Additional information

Conflict of interest The authors declare that they have no conflict of interest.

Jun Zhang was born in Auhui, China. He received his bachelor’s degree in materials science and engineering from Zhejiang University (2015). He is now a PhD student at the School of Materials Science and Engineering at Zhejiang University under the supervision of Prof. Guodong Qian. His current research interest focuses on photonic application of MOF films.

Yuanjing Cui was born in Jiangsu, China. He received his BSc and PhD in materials science and engineering from Zhejiang University in 1998 and 2006, respectively. Currently he is a full professor at the School of Materials Science and Engineering at Zhejiang University. His research interest focuses on organic-inorganic hybrid photonic materials.

Guodong Qian was born in Zhejiang, China. He received his bachelor’s (1988) and master’s (1992) degrees in materials science from Zhejiang University in China. He joined the Materials Department of Zhejiang University after obtaining his PhD degree from Zhejiang University in 1997. He was promoted to associate professor, full professor and Cheung Kong professor in 1999, 2002 and 2011, respectively. His current research interests include hybrid organic-inorganic photonic functional materials and multifunctional porous materials.

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Zhang, J., Liu, F., Gan, J. et al. Metal-organic framework film for fluorescence turn-on H2S gas sensing and anti-counterfeiting patterns. Sci. China Mater. 62, 1445–1453 (2019). https://doi.org/10.1007/s40843-019-9457-5

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