Fundamental Study of Facile and Stable Hydrogen Evolution Reaction at Electrospun Ir and Ru Mixed Oxide Nanofibers.

Electrochemical hydrogen evolution reaction (HER) has been an interesting research topic in terms of the increasing need of renewable and alternative energy conversion devices. In this article, IrxRu1-xOy (y = 0 or 2) nanofibers with diverse compositions of Ir/IrO2 and RuO2 are synthesized by electrospinning and calcination procedures. Their HER activities are measured in 1.0 M NaOH. Interestingly, the HER activities of IrxRu1-xOy nanofibers improve gradually during repetitive cathodic potential scans for HER, and then eventually reach the steady-state consistencies. This cathodic activation is attributed to the transformation of the nanofiber surface oxides to the metallic alloy. Among a series of IrxRu1-xOy nanofibers, the cathodically activated Ir0.80Ru0.20Oy shows the best HER activity and stability even compared with IrOy and RuOy, commercial Pt and commercial Ir (20 wt % each metal loading on Vulcan carbon), where a superior stability is possibly ascribed to the instant generation of active Ir and Ru metals on the catalyst surface upon HER. Density functional theory calculation results for hydrogen adsorption show that the energy and adsorbate-catalyst distance at metallic Ir0.80Ru0.20 are close to those at Pt. This suggests that mixed metallic Ir and Ru are significant contributors to the improved HER activity of Ir0.80Ru0.20Oy after the cathodic activation. The present findings clearly demonstrate that the mixed oxide of Ir and Ru is a very effective electrocatalytic system for HER.