The Deep Eutectic Solvent Precipitation Synthesis of Metastable Zn4V2O9.

A precipitation method involving a deep eutectic solvent (DES)─a mixture of hydrogen bond donor and acceptor─is used to synthesize a ternary metal oxide. Without toxic reagents, precipitates consisting of Zn3(OH)2V2O7·nH2O and Zn5(OH)6(CO3)2 are obtained by simply introducing deionized H2O to the DES solution containing dissolved ZnO and V2O5. Manipulation of the synthetic conditions demonstrates high tunability in the size/morphology of the two-dimensional nanosheets precipitated during the dynamic equilibrium process. According to differential scanning calorimetry and high-temperature powder X-ray diffraction, Zn3V2O8 and ZnO obtained by the annealing of the precipitate are intermediates in the reaction pathway toward metastable Zn4V2O9. Intimate mixing of the metal precursors achieved by the precipitation method allows access to the metastable zinc-rich vanadate with unusually rapid heat treatment. The UV-vis and surface photovoltage spectra reveal the presence of sub-band gap states, stemming from the reduced vanadium (V4+) center. Photoelectrochemical measurements confirm weak photoanodic currents for water and methanol oxidation. For the first time, this work shows the synthesis of a metastable oxide with the DES-precipitation route and provides insight into the structure-property relationship of the zinc-rich vanadate.