DFT-assisted Structure Determination of α1- and α2-VOPO4: New Insights into the Understanding of the Catalytic Performances of Vanadium Phosphates

Romain Gautier (1) , Régis Gautier (1) , Olivier J. Hernandez (1) , Nathalie Audebrand (1) , Thierry Bataille (1) , Claire Roiland (1) , Erik Elkaïm (2) , Laurent Le Pollès (1) , Eric Furet (1) , Eric Le Fur (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 SSOLEIL - Synchrotron SOLEIL

Structural investigations on vanadium phosphates, which are extensively used as catalysts in industry, often resulted in important advances in the understanding of the mechanisms driving the catalytic oxidation of light hydrocarbons. Layer translations in the two lamellar vanadium phosphates α1- and α2-VOPO4 phases identified during the catalysis were investigated by the combination of first-principles calculations, synchrotron X-ray powder diffraction, single-crystal X-ray diffraction and solid-state NMR. This analysis reveals an important feature: the α1-form is the only polymorph of VOPO4 to exhibit layer translations that prevent the formation of infinite VO6 chains. A detailed investigation of this structural characteristic in vanadium phosphates reveals the correlation between the presence of infinite VO6 chains and the catalytic performances of related phases.

Domaines: Chimie théorique et/ou physique

Romain Gautier, Régis Gautier, Olivier J. Hernandez, Nathalie Audebrand, Thierry Bataille, et al.. DFT-assisted Structure Determination of α1- and α2-VOPO4: New Insights into the Understanding of the Catalytic Performances of Vanadium Phosphates. Dalton Transactions, 2013, 42 (22), pp.8124-8131. ⟨10.1039/C3DT50217A⟩. ⟨hal-00874173⟩