ACS Omega 4 (6) 10899-10905 [2019-06-30; online 2019-06-24]
Nanostructured hydrated vanadium oxides (V2O5·nH2O) are actively being researched for applications in energy storage, catalysis, and gas sensors. Recently, a one-step exfoliation technique for fabricating V2O5·nH2O nanosheets in aqueous media was reported; however, the underlying mechanism of exfoliation has been challenging to study. Herein, we followed the synthesis of V2O5·nH2O nanosheets from the V2O5 and VO2 precursors in real time using solution- and solid-state 51V NMR. Solution-state 51V NMR showed that the aqueous solution contained mostly the decavanadate anion [H2V10O28]4- and the hydrated dioxovanadate cation [VO2·4H2O]+, and during the exfoliation process, decavanadate was formed, while the amount of [VO2·4H2O]+ remained constant. The conversion of the solid precursor V2O5, which was monitored with solid-state 51V NMR, was initiated when VO2 was in its monoclinic forms. The dried V2O5·nH2O nanosheets were weakly paramagnetic because of a minor content of isolated V4+. Its solid-state 51V signal was less than 20% of V2O5 and arose from diamagnetic V4+ or V5+.This study demonstrates the use of real-time NMR techniques as a powerful analysis tool for the exfoliation of bulk materials into nanosheets. A deeper understanding of this process will pave the way to tailor these important materials.