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Abstract

Metallization of initially insulating VO₂ via ionic liquid electrolytes, otherwise known as electrolyte gating, has recently been a topic of much interest for possible applications such as Mott transistors and memory devices. It is clear that the metallization takes place electrochemically, and, in particular, there has previously been extensive evidence for the removal of small amounts of oxygen during ionic liquid gating. Hydrogen intercalation has also been proposed, but the source of the hydrogen has remained unclear. In this work, solid-state magic angle spinning NMR spectroscopy (¹H, ²H, ¹⁷O, and ⁵¹V) is used to investigate the thermal metal–insulator transition in VO₂, before progressing to catalytically hydrogenated VO₂ and electrochemically metallized VO₂. In these experiments electrochemical metallization of bulk VO₂ particles is shown to be associated with intercalation of hydrogen, the degree of which can be measured with quantitative ¹H NMR spectroscopy. Possible sources of the hydrogen are explored, and by using a selectively deuterated ionic liquid, it is revealed that the hydrogenation is due to deprotonation of the ionic liquid; specifically, for the commonly used dialkylimidazolium-based ionic liquids, it is the “carbene” proton that is responsible. Increasing the temperature of the electrochemistry is shown to increase the degree of hydrogenation, forming first a less hydrogenated metallic orthorhombic phase then a more hydrogenated insulating Curie–Weiss paramagnetic orthorhombic phase, both of which were also observed for catalytically hydrogenated VO₂. The NMR results are supported by magnetic susceptibility measurements, which corroborate the degree of Pauli and Curie–Weiss paramagnetism. Finally, NMR spectroscopy is used to identify the presence of hydrogen in an electrolyte gated thin film of VO₂, suggesting that electrolyte breakdown, proton intercalation, and reactions with decomposition products within the electrolyte should not be ignored when interpreting the electronic and structural changes observed in electrochemical gating experiments.