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. 2020 Dec 14;5(51):33039-33046.
doi: 10.1021/acsomega.0c04526. eCollection 2020 Dec 29.

A Multifunctional Tb-MOF Detector for H2O2, Fe3+, Cr2O7 2-, and TPA Explosive Featuring Coexistence of Binuclear and Tetranuclear Clusters

Hong-Mei Chai  1 , Gang-Qiang Zhang  1 , Chun-Xia Jiao  1 , Yi-Xia Ren  1 , Lou-Jun Gao  1
Affiliations

A Multifunctional Tb-MOF Detector for H2O2, Fe3+, Cr2O7 2-, and TPA Explosive Featuring Coexistence of Binuclear and Tetranuclear Clusters

Hong-Mei Chai et al. ACS Omega. .

Abstract

A novel three-dimensional microporous terbium(III) metal-organic framework (Tb-MOF) named as [Tb10 (DBA)6(OH)4(H2O)5]·(H3O)4 (1), was successfully obtained by a solvothermal method based on terbium nitrate and 5-di(2',4'-dicarboxylphenyl) benzoic acid (H5DBA). The Tb-MOF has been characterized by single crystal X-ray diffraction, elemental analysis, thermogravimetry, and fluorescence properties, and the purity was further confirmed by powder X-ray diffraction (PXRD) analysis. Structural analysis shows that there are two kinds of metal cluster species: binuclear and tetranuclear, which are linked by H5DBA ligands in two μ7 high coordination fashions into a three-dimensional microporous framework. Fluorescence studies show that the Tb-MOF can detect H2O2, Fe3+, and Cr2O7 2- with high sensitivity and selectivity and can also be used for electrochemical detection of exposed 2,4,6-trinitrophenylamine (TPA) in water. The highly selective and sensitive detection ability of the Tb-MOF might make it a potential multifunctional sensor in the future.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) Coordination environment of Tb1–Tb4 (symmetry codes: a: 4/3-y,2/3+x-y,-1/3+z; b: 1-x+y,1-x,z; c: 1/3+x,-1/3+y,-4/3+z; d: 4/3-y,2/3+x-y,2/3+z; e: 1-x+y,1-x,-2+z; f: 1-x+y,1-x,-1+z). (b) Six-angle group based on one tetranuclear cluster, six DBA ligands, and binuclear units. (c) 3D microporous framework. (d) Topology of 3D.
Scheme 1
Scheme 1. Coordination Modes of DBA5– Ligands in Complex 1(a) and (b)
Figure 2
Figure 2
PXRD patterns of the Tb-MOF (simulated, determination, and after sensing performances of H2O2, Fe3+, and Cr2O72–).
Figure 3
Figure 3
TGA curve of complex 1.
Figure 4
Figure 4
Solid-state fluorescence spectra of the Tb-MOF and H5L (λex = 351 nm) and 3D photoluminescence spectra of the Tb-MOF.
Figure 5
Figure 5
(a) Luminescence spectra and histogram of the Eu-MOF introduced into various solvents, λex = 351 nm. (b) Luminescence spectra of the Tb-MOF with H2O2 at different concentrations in a water solution.
Figure 6
Figure 6
(a) Luminescence spectra and histogram of the Tb-MOF introduced into different metal ions (λex = 351 nm). (b) Luminescence spectra of the Tb-MOF in different concentrations of Fe3+ ions.
Figure 7
Figure 7
Interference of metal ions with Tb-MOF fluorescence sensing Fe3+.
Figure 8
Figure 8
(a) Luminescence spectra and histogram of the Tb-MOF introduced into different inorganic anions (λex = 351 nm). (b) Luminescence spectra of the Tb-MOF in different concentrations of Cr2O72–.
Figure 9
Figure 9
Tb-MOF/CPE by cyclic voltammetry-detected TNP.
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