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Insights into substitution effects and reactivity of Lindqvist-type polyoxometalates from DFT calculations

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Abstract

In this work, the geometric and electronic parameters of pure and vanadium-substituted anions of Lindqvist polyoxometalates have been investigated using DFT calculations. Active sites of all anions are identified through results on local and global reactivity descriptors. The results indicate that bridging oxygen atoms in all clusters are the most active sites. Using this, the mechanism of the catalytic generation of the hydroxyl radical from water was studied for the di-substituted Lindqvist polyoxometalate [V2Mo4O19]4−. This study provides a detailed understanding of this important intermediate step in photo-oxidation reactions. The mechanistic route makes it possible to locate transition states and intermediates structures and demonstrates that the pre-association of the water molecule leads to an H abstraction with an energy barrier of 26.42 kcal/mol and OH radical and [HV2Mo4O19]4− as products in this step.

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Authors and Affiliations

  1. Laboratoire de Chimie Théorique Computationnelle Et Photonique, Faculté de Chimie, Université Des Sciences Et de La Technologie Houari-Boumédiène (USTHB), El Alia, BP32, 16111, Algiers, Algeria

    Meriem Nassar & Amar Saal

  2. LCAGC Laboratoire, Université Mouloud Mammeri Tizi Ouzou, UMMTO, 15000, Tizi-Ouzou, Algeria

    Amar Saal

  3. SDU-ANU Joint Science College, Shandong University, Weihai, 264209, People’s Republic of China

    Meijuan Zhou

  4. Laboratory of Theoretical Chemistry, Department of Chemistry, Namur Institute of Structured Matter (NISM), University of Namur, Rue de Bruxelles 61, 5000, Namur, Belgium

    Michael Springborg

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  4. Michael Springborg
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Contributions

All authors contributed to the article and approved the contents of the manuscript. M.N. and M.Z. performed the computational calculations. M.N. performed the interpretations and the first draft of the manuscript. A.S., M.S. and M.Z. edited and reviewed the manuscript.

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Correspondence to Meriem Nassar.

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Nassar, M., Saal, A., Zhou, M. et al. Insights into substitution effects and reactivity of Lindqvist-type polyoxometalates from DFT calculations. Struct Chem (2023). https://doi.org/10.1007/s11224-023-02236-7

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