Citation: Chunhui Zhang, Jie Wang, Jieyang Zhan, Runmin Yang, Guanggang Gao, Jiayuan Zhang, Linlin Fan, Mengqi Wang, Hong Liu. Highly sensitive hydrazine detection through a novel Raman scattering quenching mechanism enabled by a crystalline and noble metal–free polyoxometalate substrate[J]. Chinese Chemical Letters, ;2025, 36(3): 109719. doi: 10.1016/j.cclet.2024.109719 shu

Highly sensitive hydrazine detection through a novel Raman scattering quenching mechanism enabled by a crystalline and noble metal–free polyoxometalate substrate

School of Materials Science and Engineering, University of Jinan, Ji'nan 250022, China

mse_gaogg@ujn.edu.cn

mse_fanll@ujn.edu.cn

mse_liuh@ujn.edu.cn

Received Date: 12 December 2023
Revised Date: 6 February 2024
Accepted Date: 1 March 2024
Available Online: 11 March 2024

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In the field of Raman spectroscopy detection, the quest for a non–noble metal, recyclable, and highly sensitive detection substrate is of utmost importance. In this work, a new crystalline and noble metal–free substrate of [Bi(DMF)₈][PMo₁₂O₄₀] (Bi–PMo₁₂) is designed, which is composed of [PMo₁₂O₄₀]³⁻ and solvated [Bi(DMF)₈]³⁺ cations. Mechanistic studies have revealed that Raman scattering quenching phenomenon arises from two main factors. Firstly, it arises from the absorption of the scattered light due to the transition of a single electron in the reduced state of Mo^V between 4d orbitals. Secondly, after the interaction between the substrate and hydrazine, the surface undergoes varying degrees of roughening, leading to an impact on the scattered light intensity. These two effects collectively contribute to the detection of low concentrations of N₂H₄. As a result, Bi–PMo₁₂ opens up a novel Raman scattering quenching mechanism to realize the detection of reduced N₂H₄ small molecules. A remarkably low detection limit of 4.5 × 10⁻⁹ ppm for N₂H₄ is achieved on the Bi–PMo₁₂ substrate. This detection has a lower concentration than the currently known SERS detection of N₂H₄. Moreover, Bi–PMo₁₂ can be recovered and reused through recrystallization, achieving a recovery rate of up to ca. 51%. This study reveals the underlying potential of crystalline polyoxometalate materials in the field of Raman detection, thus opening up new avenues for highly sensitive analysis using Raman techniques.
- Polyoxometalate,
- Hydrazine,
- Raman detection,
- Quenching,
- Single crystal
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