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 Jun 2021
Accepted
03 Aug 2021
First published
03 Aug 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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