Efficient Electrochemical Water Splitting with PdSn4 Dirac Nodal Arc Semimetal

Recently, several researchers have claimed the existence of superior catalytic activity associated with topological materials belonging to the class of Dirac/Weyl semimetals, owing to the high electron conductivity and charge carrier mobility in these topological materials. By means of X-ray photoelectron spectroscopy, electrocatalytic tests, and density functional theory, we have investigated the chemical reactivity (chemisorption of ambient gases), ambient stability, and catalytic properties of PdSn4, a topological semimetal showing Dirac node arcs. We find a Tafel slope of 83 mV in the hydrogen evolution reaction (HER) dec-1with an overpotential of 50 mV, with performances resembling those of pure Pd, regardless of its limited amount in the alloy, with a subsequent reduction in the cost of raw materials by ∼80%. Remarkably, the PdSn4-based electrode shows superior robustness to CO compared to pure Pd and Pt and high stability in water media, although the PdSn4surface is prone to oxidation with the formation of a sub-nanometric SnO2skin. Moreover, we also assessed the significance of the role of topological electronic states in the observed catalytic properties. Actually, the peculiar atomic structure of oxidized PdSn4enables the migration of hydrogen atoms through the Sn-O layer with a barrier comparable with the energy cost of the Heyrovsky step of HER over Pt(111) in acidic media (0.1 eV). On the other hand, the topological properties play a minor role, if existing, contrarily to the recent reports overestimating their contribution in catalytic properties. © 2021 The Authors. Published by American Chemical Society D.W.B. acknowledges the support from the Ministry of Science and Higher Education of the Russian Federation (through the basic part of the government mandate, project no. FEUZ-2020-0060 and Jiangsu Innovative and Entrepreneurial Talents Project). A.M., J.F., and F.V. acknowledge the Italian Ministry of University and Research MUR by the PRIN 2017 (no. 2017YH9MRK) and MISE FISR 2019 AMPERE (FISR2019_01294) projects for the financial support.