Issue 19, 2021

Tandem-like vanadium cluster chains in a polyoxovanadate-based metal–organic framework for efficient catalytic oxidation of sulfides

Abstract

A novel polyoxovanadate-based metal–organic framework (POV-MOF), [Ni(bix)2]{V4O11} (V-Ni-MOF, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), was successfully synthesized and structurally characterized. Single crystal X-ray diffraction analysis shows that the {V4} clusters in V-Ni-MOF are composed of four VO4 tetrahedra and further connected into a tandem-like chain. The unique vanadium chains with high-density coordinatively unsaturated vanadium centers in V-Ni-MOF can efficiently catalyze the oxidation of sulfides, where sulfides were completely converted to sulfones with the mild oxidant hydrogen peroxide within 1 hour at 40 °C. To our knowledge, most POV-MOFs could efficiently catalyze the oxidation of sulfides only when a stronger oxidant such as tert-butyl hydroperoxide was used. We attempted to utilize density functional theory (DFT) calculations to explore the reason for the high activity of V-Ni-MOF under mild hydrogen peroxide. DFT calculations indicated that the tandem-like vanadium cluster chain has a lower lowest unoccupied molecular orbital (LUMO) energy level compared to a discrete vanadium cluster, which matches better with the highest occupied molecular orbital (HOMO) energy level of hydrogen peroxide to generate active peroxo-POV species. In addition, as a stable heterogeneous catalyst, V-Ni-MOF sustainably maintains an excellent catalytic activity after multiple cycles.

Graphical abstract: Tandem-like vanadium cluster chains in a polyoxovanadate-based metal–organic framework for efficient catalytic oxidation of sulfides

Supplementary files

Article information

Article type
Research Article
Submitted
25 6 2021
Accepted
03 8 2021
First published
03 8 2021

Inorg. Chem. Front., 2021,8, 4367-4375

Tandem-like vanadium cluster chains in a polyoxovanadate-based metal–organic framework for efficient catalytic oxidation of sulfides

T. Dang, R. Li, H. Tian, Q. Wang, Y. Lu and S. Liu, Inorg. Chem. Front., 2021, 8, 4367 DOI: 10.1039/D1QI00799H

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