Photocatalytic Properties and Luminescent Sensing for Cr3+ Cations of Polyoxovanadates-Based Inorganic–Organic Hybrid Compounds with Multiple Lewis Basic Sites

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Key Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China
School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian 223300, People’s Republic of China
*E-mail: [email protected] (J.Y.).
*E-mail: [email protected]. Fax: +86-431-85098620 (J.-F.M).
Cite this: Cryst. Growth Des. 2016, 16, 1, 265–276
Publication Date (Web):December 21, 2015
https://doi.org/10.1021/acs.cgd.5b01226
Copyright © 2015 American Chemical Society
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Abstract

A new family of polyoxovanadates-based inorganic–organic hybrid compounds with multiple Lewis basic sites, namely, [Zn5(Htrb)2(H2O)2(V5O15)2]·11H2O (1), [Zn2(Htrb)(HV5O15)]·6H2O (2), [Co3(Htrb)(H2O)4(V3O9)2]·4H2O (3), and [Ag3(Htrb)(H4V5O16)]·H2O (4), have been hydrothermal synthesized by using a multidentate N-containing hexakis(1,2,4-triazol-ylmethy1)benzene (Htrb). In 1, [V4O12]4– and [V6O18]6– rings are linked by Zn(II) ions into a two-dimensional (2D) inorganic layer, which are pillared by Htrb ligands to afford a unique three-dimensional (3D) framework. In 2, rod-shaped [H2V10O30]8– clusters are bridged by Zn(II) ions to generate one-dimensional inorganic hybrid motifs, which are joined by Htrb ligands to yield a 3D framework. In 3, Co(II) ions bridge [V6O18]6– rings to result in a 2D inorganic sheet, and the adjacent sheets are extended by the Htrb ligands into a 3D motif. In 4, adjacent 12-membered vanadium rings, composed of [VO4] tetrahedra and [VO5] trigonal bipyramids, form a unique 2D inorganic layer via sharing corner O atoms. Strikingly, neighboring layers are further extended by Htrb ligands and Ag(I) ions into a 3D framework. Moreover, photocatalytic degradation of compounds 1, 3, and 4 toward methylene blue (MB) and methyl orange (MO) was studied under UV light irradiation. A possible photocatalytic mechanism was also speculated by introducing t-butyl alcohol as a widely used ·OH scavenger. In addition, luminescent selective and sensitive sensing of Cr3+ compared with other metal ions such as Zn2+, Al3+, Co2+, K+, Na+, and Pb2+ were investigated by using 1 and 4. Finally, their electrochemical behaviors were also studied.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.5b01226.

  • Experimental section, selected bond lengths and angles, coordination modes of the Htrb ligands in 14, the proposed photodegradation mechanism of MB with 1 as catalyst under UV light irradiation, absorption spectra of the MO and MB solutions during the decomposition reaction under UV irradiation without any catalyst, absorption spectra of the MB solution during the decomposition reaction in the presence of 1/TAB and photocatalytic decomposition of MB solution under UV with the use of compound 1 and 1 in the presence of TAB, emission spectra of compounds 1 and 4, TG curve of compounds 2 and 4 (PDF)

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