Issue 88, 2020

Oxygen-atom vacancy formation and reactivity in polyoxovanadate clusters

Abstract

Reducible metal oxides (RMOs) are widely used materials in heterogeneous catalysis due to their ability to facilitate the conversion of energy-poor substrates to energy-rich chemical fuels and feedstocks. Theoretical investigations have modeled the role of RMOs in catalysis and found they traditionally follow a mechanism in which the generation of oxygen-atom vacancies is crucial for the high activity of these solid supports. However, limited spectroscopic techniques for in situ analysis renders the identification of the reactivity of individual oxygen-atom vacancies on RMOs challenging. These obstacles can be circumvented through the use of homogeneous complexes as molecular models for metal oxides, such as polyoxometalates. Summarized herein, a sub-class of polyoxometalates, polyoxovanadate–alkoxide clusters, ([V6O7(OR)12]n; R = CH3, C2H5; n = 2−, 1−, 0), are explored as homogeneous molecular models for bulk vanadium oxide. A series of synthetic strategies have been employed to access oxygen-deficient vanadium oxide assemblies, including addition of V(Mes)3(thf), tertiary phosphanes, and organic acids to plenary Lindqvist motifs. We further detail investigations surrounding the ability of these oxygen-deficient sites to mediate reductive transformations such as O2 and NOx1− (x = 2, 3) activation.

Graphical abstract: Oxygen-atom vacancy formation and reactivity in polyoxovanadate clusters

Article information

Article type
Feature Article
Submitted
01 Sep 2020
Accepted
05 Oct 2020
First published
05 Oct 2020

Chem. Commun., 2020,56, 13477-13490

Author version available

Oxygen-atom vacancy formation and reactivity in polyoxovanadate clusters

B. E. Petel and E. M. Matson, Chem. Commun., 2020, 56, 13477 DOI: 10.1039/D0CC05920J

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