Mapping the electrocatalytic water splitting activity of VO₂ across its insulator-to-metal phase transition

The electrocatalytic water splitting activity of V-based oxides has been rarely investigated, even though several polymorphs in VO₂ are expected to exhibit different electrocatalytic activities depending on their crystal and electronic structures. The rutile structure of VO₂(R), showing metallic character, is a good candidate for a new electrocatalyst since it undergoes insulator-to-metal transition (IMT) from the insulating VO₂(M1) at a low temperature of 68 °C, and involves a substantially increased electrical conductivity by three orders of magnitude. The extensive improvements in the electrocatalytic activity for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) are confirmed when the IMT is induced where the overpotential (η₁₀) is reduced from 1056 mV to 598 mV in the OER and 411 mV to 136 mV in the HER, respectively. This improvement is attributed to the increased electrochemically active surface area (ECSA), reduced charge transfer resistance, and increased electron density, driven by the IMT to the metallic VO₂(R) phase.