Hollow TiO2 Supports for Enhanced Acidic Oxygen Evolution Activity

Abstract

The usage of scarce and expensive iridium as a catalyst for the acidic oxygen evolution reaction (OER) represents a significant barrier to up-scaling the deployment of proton exchange membrane water electrolysers (PEM-WEs). Accordingly, strategies such as nanostructuring catalysts to increase the electrochemical surface area (e.g. nanoparticles, single-atom catalysts, nanoclusters) as well as investigating mixed metal alloys and oxides (e.g. perovskites, pyrochlores) have been developed with promising half-cell performances. One further approach that has recently gained attention is the deployment of catalyst-supports whereby a high surface area support is used to scaffold the dispersed iridium catalyst.1 Analogous to the selection of a catalyst, the catalyst support must withstand the highly corrosive and oxidising conditions of a PEM-WE anode. Thus, metal oxides such as titanium dioxide are commonly deployed as catalyst-supports for acidic OER. The catalyst-support moiety must also be sufficiently conductive when integrated into the PEM-WE catalyst layers. Otherwise, the cell voltages required to generate sufficient activity will render the device impractical. Accordingly, strategies such as doping, or the addition of conductive layers between the catalyst and support have been investigated.2 In this study we investigate a unique support morphology that affords promising OER activity and stability in acidic electrolyte with high iridium mass activities. Specifically, we deploy a hollow TiO2 catalyst support,3 coated with a Au/Pd interlayer to provide electrical conductivity. The OER activity and stability is initially screened in a rotating disk electrode (RDE) configuration as a function of thermal treatments (reducing vs oxidising) as well as with at various Au/Pd (1 – 5 wt%) and Ir loadings (35 – 50 wt%). Our highest performing catalyst have a mass activity of around 480 A/gIr at 1.60 V vs RHE. The catalysts are subsequently investigated in a membrane electrode assembly (MEA) and subject to 10k accelerated stress test stability measurements. To understand the role of the support morphology, Au/Pd interlayer and iridium loadings on electrochemical performance, we also characterise the synthesised catalysts by (scanning) transmission electron microscopy (STEM/TEM), X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS) and electrical conductivity measurements. Collectively, we report the critical role of the Au/Pd interlayer to enable such high electrochemical performance. We also show that the hollow structure of the TiO2 support may be enhancing mass transport in the catalyst layers. References 1 A. S. Pushkarev, I. V Pushkareva and D. G. Bessarabov, Energy & Fuels, 2022, 36, 6631–6625.2 Y. N. Regmi, E. Tzanetopoulos, G. Zeng, X. Peng, D. I. Kushner, T. A. Kistler, L. A. King and N. Danilovic, ACS Catal., 2020, 10, 13125–13135.3 U. S. Jonnalagadda, X. Su and J. J. Kwan, Ultrason. Sonochem., 2021, 73, 105530.