Abstract
NiMo alloys are considered highly promising non-noble Hydrogen Evolution Reaction (HER) catalysts. Besides the synergistic effect of alloying elements, recent attention is drawn to the Mo leaching from the catalyst. This work investigates the role of Mo in NiMo alloys during HER, aiming to understand the interplay between compositional, structural, and electronic factors on the activity, and their effects on the electrode material and catalyst properties. For this purpose, sputter-deposited low roughness NixMo100-x thin films are produced. The investigation of catalyst performance depending on their chemical composition shows a volcano-shaped plot, peaking for the Ni65Mo35 alloy with the highest intrinsic activity in alkaline HER. A comprehensive electrode surface analysis combining transmission electron microscopy, X-ray photoelectron spectroscopy and atomic force microscopy identifies the leaching of Mo on a structural level and indicates the formation of a Ni(OH)2-rich surface area. The ultimate surface characteristics of the NiMo catalysts depend on the initial composition and the electrochemical procedure. Based on the findings, it conclude that the observed catalytic properties of NiMo alloys in HER are determined by a complex interplay of increasing roughness, available surface species and their synergies. The leaching of Mo has a proven structural effect and is considered one of several factors contributing to the enhanced catalyst activity.
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