A stable lanthanum-based metal-organic framework as fluorescent sensor for detecting TNP and Fe3+ with hyper-sensitivity and ultra-selectivity

Maoquan Wu; Hongxia Zhang; Chunyu Ge; Jie Wu; Shouchun Ma; Ye Yuan; Liyan Zhao; Tongjie Yao; Xiao Zhang; Qingfeng Yang

doi:10.1016/j.saa.2021.120276

A stable lanthanum-based metal-organic framework as fluorescent sensor for detecting TNP and Fe³⁺ with hyper-sensitivity and ultra-selectivity

Spectrochim Acta A Mol Biomol Spectrosc. 2022 Jan 5:264:120276. doi: 10.1016/j.saa.2021.120276. Epub 2021 Aug 19.

Authors

Maoquan Wu¹, Hongxia Zhang¹, Chunyu Ge¹, Jie Wu², Shouchun Ma¹, Ye Yuan³, Liyan Zhao¹, Tongjie Yao¹, Xiao Zhang⁴, Qingfeng Yang⁵

Affiliations

¹ MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, People's Republic of China.
² Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China. Electronic address: [email protected].
³ Center for Analysis, Measurement and Computing, Harbin Institute of Technology, Harbin, People's Republic of China.
⁴ MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, People's Republic of China. Electronic address: [email protected].
⁵ State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, People's Republic of China. Electronic address: [email protected].

PMID: 34455379
DOI: 10.1016/j.saa.2021.120276

Abstract

A new Lanthanum-based luminescent metal-organic framework, {[La(H₂O)₄(HL)]·H₂O} (1), has been successfully synthesized by employing 3,3',5,5'-azodioxybenzenetetracarboxylic acid (H₄L) as a rigid organic linker through the solvothermal reactions. 1 exhibits a two-dimensional (2D) layered structure and a three-dimensional (3D) supramolecular structure is formed by hydrogen bonds between the layers. Stability studies indicate that 1 has good chemical stability and thermostability. Meanwhile, the K_sv values for TNP is 4.61 × 10⁴ M^-1 with the LOD of 4.13 × 10^-6 M and the K_sv value for Fe³⁺ is 1.22 × 10⁴ M^-1 with the LOD of 1.72 × 10^-5 M, respectively, which demonstrated that 1 exhibits high sensitivity and excellent selectivity for the detection of TNP and Fe³⁺via fluorescence quenching. Significantly, 1 shows high regenerability after five recycling progress for sensing Fe³⁺. The possible mechanisms associated with the luminescent quenching are discussed in detail through some relevant experiments and tests, as well as the DFT calculations. Based on the above excellent properties of 1, it will have extremely potential to be used as a dual functional sensor for both detecting TNP and Fe³⁺ in aqueous solution, simultaneously.

Keywords: Crystal structure; Fe(3+); Fluorescent sensor; Metal-organic framework; TNP.