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Intercalation chemistry of layered vanadyl phosphate: a review

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Abstract

The intercalation chemistry of layered αI modification of vanadyl phosphate and vanadyl phosphate dihydrate is reviewed. The focus is on neutral molecular guests and on metal cations used as guest species. The basic condition for the ability of the neutral molecules to be intercalated into vanadyl phosphate is a presence of an electron donor atom in them. The most commonly used guest compounds are those containing oxygen, nitrogen or sulfur as electron donor atoms. Regarding the molecules containing oxygen, various compounds were used as molecular guests starting from water to alcohols, ethers, aldehydes, ketones, carboxylic acids, lactones, and esters. An arrangement of the guest molecules in the interlayer space is discussed in connection with the data obtained by powder X-ray diffraction, thermogravimetry, IR and Raman spectroscopies, and solid-state NMR. In some cases, the local structure was suggested on the basis of quantum chemical calculations. Besides of those O-donor guests, also N-donor guests such as amines, nitriles and nitrogenous heterocycles and S-donor guests such as tetrathiafulvalene were intercalated into VOPO4. Also intercalates of complexes like ferrocene were prepared. Intercalation of cations is accompanied by a reduction of vanadium(V) to vanadium(IV). In this kind of intercalation reactions, an iodide of the intercalated cation is often used as it serves both as a mild reduction agent and as a source of the intercalated species. Intercalates of alkali metals, hydronium and ammonium were prepared and characterized. In the case of lithium and sodium intercalates, a staging phenomenon was observed. These redox intercalated vanadyl phosphates undergo ion exchange reactions which are discussed from the point of the nature of cations involved in the exchange. Vanadyl phosphates in which a part of vanadium atom is replaced by other metals are also briefly reviewed.

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Acknowledgment

This work was supported by the Academy of Sciences of the Czech Republic (AV0Z40500505) and the Ministry of Education, Youth and Sports of the Czech Republic (MSM 0021627501).

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  1. Ludvík Beneš, Klára Melánová, Jan Svoboda & Vítězslav Zima

    Present address: Joint Laboratory of Solid State Chemistry, Studentská 95, 532 10, Pardubice, Czech Republic

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  1. Faculty of Chemical Technology, University of Pardubice, Studentská 95, 532 10, Pardubice, Czech Republic

    Ludvík Beneš

  2. Institute of Macromolecular Chemistry of Academy of Sciences, v.v.i., Heyrovský Sq. 2, 120 06, Prague, Czech Republic

    Klára Melánová, Jan Svoboda & Vítězslav Zima

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Beneš, L., Melánová, K., Svoboda, J. et al. Intercalation chemistry of layered vanadyl phosphate: a review. J Incl Phenom Macrocycl Chem 73, 33–53 (2012). https://doi.org/10.1007/s10847-011-0097-1

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