Copper-containing hybrid compounds based on extremely rare [V2Mo6O26]6– POM as water oxidation catalysts

Halyna I. Buvailo; Valeriya G. Makhankova; Vladimir N. Kokozay; Irina V. Omelchenko; Svitlana V. Shishkina; Julia Jezierska; Mariia V. Pavliuk; Sergii I. Shylin

doi:10.1039/C9QI00040B

Copper-containing hybrid compounds based on extremely rare [V₂Mo₆O₂₆]^6– POM as water oxidation catalysts†

Halyna I. Buvailo,^a Valeriya G. Makhankova,

*^a Vladimir N. Kokozay,^a Irina V. Omelchenko,

^b Svitlana V. Shishkina,

^b Julia Jezierska,^c Mariia V. Pavliuk^d and Sergii I. Shylin

*^d

Author affiliations

* Corresponding authors

^a Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska 64/13, 01601 Kyiv, Ukraine
E-mail: leram@univ.kiev.ua

^b Institute for Single Crystals, National Academy of Sciences of Ukraine, Nauky Ave 60, 61001 Kharkiv, Ukraine

^c Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wroclaw, Poland

^d Department of Chemistry – Ångström Laboratory, Uppsala University, P.O. Box 523, 75120 Uppsala, Sweden
E-mail: sergii.shylin@kemi.uu.se

Abstract

Herein, we report two approaches to the synthesis of heterometallic complexes (NH₄)_2n(H₂en)_n{[Cu(en)₂][α-V₂Mo₆O₂₆]}·4nH₂O (1), (NH₄)₂{[Cu(dien)(H₂O)]₂[α-V₂Mo₆O₂₆]}·5H₂O (2) and (NH₄)₂{[Cu(dien)(H₂O)]₂[α-V₂Mo₆O₂₆]}·8H₂O (3) that have been employed in homogeneous photochemical oxidation of water to dioxygen. In these hybrid metalorganic–inorganic compounds, copper-containing complex fragments are covalently bound to the rare vanadium-disubstituted α-octamolybdate cluster. They exhibit variable catalytic activity controlled by the local coordination environment of copper reaching a notably high turnover frequency of 0.24 s⁻¹ for 3 in combination with a relatively low water oxidation overpotential. The complexes have been also used as precursors for the preparation of mixed oxide phases that have proven to be active heterogeneous water oxidation catalysts.

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Article information

DOI: https://doi.org/10.1039/C9QI00040B
Article type: Research Article
Submitted: 10 Jan 2019
Accepted: 25 May 2019
First published: 29 May 2019
This article is Open Access

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Inorg. Chem. Front., 2019,6, 1813-1823

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Copper-containing hybrid compounds based on extremely rare [V₂Mo₆O₂₆]^6– POM as water oxidation catalysts

H. I. Buvailo, V. G. Makhankova, V. N. Kokozay, I. V. Omelchenko, S. V. Shishkina, J. Jezierska, M. V. Pavliuk and S. I. Shylin, Inorg. Chem. Front., 2019, 6, 1813 DOI: 10.1039/C9QI00040B

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