Data for Thermal transformation of V+Bi+Zn single-source precursors: identification of amorphous intermediates and a new kinetic phase of BiVO4

Molecular single-source precursors are a promising way of obtaining multi-element extended solids directly. We show that thermal decomposition of well-defined mono-, bi- and trimetallic polyoxovanadates (POVs) proceeds through a series of intermediate amorphous and crystalline species which we characterize using solid-state NMR spectroscopy, Pair-Distribution Function (PDF) analysis and in-situ X-ray diffraction, before forming crystalline V2O5 and BiVO4 products. This synthetic strategy enables the formation of phases inaccessible using other routes including a previously unknown polymorph of BiVO4 which we name β-BiVO4 due to its similarity to β-SnWO4. Local structure information also reveals the temperature dependent incorporation of Zn dopants into BiVO4. The study also explores the electrochemical properties of new amorphous mixed-valence vanadium oxides as Li-ion battery electrodes. We suggest that careful analysis of the thermal decomposition of molecular species may be a way of obtaining hitherto unknown kinetically stabilized polymorphs and amorphous variants of extended solids. IR and UV-vis spectroscopy, powder X-ray diffraction, X-ray pair distribution function data, thermogravimetric analysis of precursors and products following annealing of precursors as described in the associated publication. XANES of 1 and 1 heated to 200 degrees vs vanadium standards. Electrochemical data of 1_200 as described in associated publication.