Strong Catalyst-Support Interaction in WOx Nanowires Supported Iridium Nanocatalysts: A Pathway to Efficient Water Electrolysis

Abstract

This paper investigates the use of sub-stoichiometric tungsten oxide nanowires (WOxNW) as a support material for Ir nanocatalysts in the oxygen evolution reaction (OER) for proton exchange membrane water electrolysis (PEMWE). The results demonstrate that Ir@WOxNW has exceptional activity and durability, which paves the way for large-scale PEMWE deployment. The catalyst-support interaction plays a crucial role in explaining this performance boost.The preparation and characterization of Ir@WOxNW involved loading ultra-fine Ir nanoparticles onto WOxNW through hydrothermal treatment. High-resolution transmission electron microscopy (HR-TEM) and energy-dispersive X-ray spectroscopy (EDS) mapping analysis revealed that the iridium nanoparticles were uniformly loaded on the WOxNW support material, indicating efficient loading and dispersion. X-ray photoelectron spectroscopy (XPS) analysis showed that the supported Ir catalysts had a mixed valence state of Ir0 and Ir4+. Ir@WOxNW was compared with three other Ir-based OER catalysts, outperforming them in terms of activity and durability.The Ir@WOxNW catalyst demonstrated superior OER activity compared to the other three catalysts, with a mass activity of 812 A/gIr at 1.55 V vs reversible hydrogen electrode (RHE). The Tafel slopes of the OER catalysts were grouped into two categories: Ir Black and Ir@WOxNW showed smaller values (about 40 mV/dec), and larger values for Ir@ATO and Ir Oxide (about 120 mV/dec), respectively. Electrochemical impedance spectroscopy (EIS) measurements indicated that the high mass activity of Ir@WOxNW was due to a high population of catalytic sites with fast intrinsic kinetics from the dispersed ultra-fine Ir catalyst on WOxNW. The durability of all catalysts was investigated using an accelerated durability test (ADT), and the Ir@WOxNW catalyst demonstrated unexpectedly high durability compared to the other catalysts.The postmortem XPS analysis showed that the Ir@WOxNW catalyst exhibited a subtle change in Ir0/Ir4+ ratio after the ADT, indicating suppressed Ir oxidation and greater stability compared to the other catalysts. Additionally, non-destructive depth profile analysis by synchrotron based XPS was conducted on the supported ultrafine Ir catalysts before and after the ADT test. The difference in oxidation state increased as the supported Ir catalysts were probed deeper into the core. The results showed that after oxidation potential cycles ADT, the WOxNW-supported Iridium exhibited strong resistance to oxidation. The core location remained a high percentage of metal peak, in contrast to the other three control catalysts.Density functional theory calculations suggested that the oxygen-deficient WOxNW support helps to maintain the OER-active metal@metal oxide core@shell-like form of the Ir catalyst particles by enhancing electron transfer from the WOxNW to the Ir surface, thereby weakening the binding of oxygen to the Ir surface and enhancing the oxidation resistance of the Ir metal to oxides.In conclusion, ultrafine Ir nanoparticles supported on WOxNW have significant potential for practical applications in electrochemical water splitting. The high activity and durability of Ir@WOxNW make it a promising candidate for large-scale PEMWE deployment.