Analysis and Prediction of Stacking Sequences in Intercalated Lamellar Vanadium Phosphates

Romain Gautier (1) , Yoann Fourré , Eric Furet (2) , Régis Gautier (2) , Eric Le Fur (2)

1 IMN - Institut des Matériaux Jean Rouxel
2 ISCR - Institut des Sciences Chimiques de Rennes

An approach is presented that enables the analysis and prediction of stacking sequences in intercalated lamellar vanadium phosphates. A comparison of previously reported vanadium phosphates reveals two modes of intercalation: (i) 3d transition metal ions intercalated between VOPO4 layers and (ii) alkali/alkaline earth metal ions between VOPO4·H2O layers. Both intercalations were investigated using DFT calculations in order to understand the relative shifts of the vanadium phosphate layers. These calculations in addition to an analysis of the stacking sequences in previously reported materials enable the prediction of the crystal structures of Mx(VOPO4)·yH2O (M = Cs+, Cd2+ and Sn2+). Experimental realization and structural determination of Cd(VOPO4)2·4H2O by single-crystal X-ray diffraction confirmed the predicted stacking sequences.

Mots clés: cadmium vanadyl phosphate prepn crystal structure; Density functional calculations; Hydrothermal synthesis; stacking sequence analysis metal intercalated lamellar vanadium phosphate; Stacking sequences; Vanadium phosphates

Domaines: Chimie

Romain Gautier, Yoann Fourré, Eric Furet, Régis Gautier, Eric Le Fur. Analysis and Prediction of Stacking Sequences in Intercalated Lamellar Vanadium Phosphates. European Journal of Inorganic Chemistry, 2015, 2015 (11), pp.1941--1945. ⟨10.1002/ejic.201403210⟩. ⟨hal-01153402⟩