Nanostructured metal hydrides are able to efficiently detect hydrogen in optical sensors. In the literature, two nanostructured systems based on metal hydrides have been proposed for this purpose each with its own detection principle: continuous sub-100 nm thin films read out via optical reflectance/transmittance changes and nanoparticle arrays for which the detection relies on localized surface plasmon resonance. Despite their apparent similarities, their optical and structural response to hydrogen has never been directly compared. In response, for the case of Pd1−yAuy (y = 0.15−0.30) alloys, we directly compare these two systems and establish that they are distinctively different. We show that the dissimilar optical response is not caused by the different optical readout principles but results from a fundamentally different structural response to hydrogen due to the different nanostructurings. The measurements empirically suggest that these differences cannot be fully accounted by surface effects but that the nature of the film−substrate interaction plays an important role and affects both the hydrogen solubility and the metal-to-metal hydride transition. In a broader perspective, our results establish that the specifics of nanoconfinement dictate the structural properties of metal hydrides, which in turn control the properties of nanostructured devices including the sensing characteristics of optical hydrogen sensors and hydride-based active plasmonic systems.@en

Catalyzing capping layers on metal hydrides are employed to enhance the hydrogenation kinetics of metal hydride-based systems such as hydrogen sensors. Here, we use a novel experimental method to study the hydrogenation kinetics of catalyzing capping layers composed of several alloys of Pd and Au as well as Pt, Ni, and Ru, all with and without an additional PTFE polymer protection layer and under the same set of experimental conditions. In particular, we employ a thin Ta film as an optical indicator to study the kinetics of the catalytic layers deposited on top of it and which allows one to determine the absolute hydrogenation rates. Our results demonstrate that doping Pd with Au results in significantly faster hydrogenation kinetics, with response times up to five times shorter than Pd through enhanced diffusion and a reduction in the activation energy. On the other hand, the kinetics of non-Pd-based materials turn out to be significantly slower and mainly limited by the diffusion through the capping layer itself. Surprisingly, the additional PTFE layer was only found to improve the kinetics of Pd-based capping materials and has no significant effect on the kinetics of Pt, Ni, and Ru. Taken together, the experimental results aid in rationally choosing a suitable capping material for the application of metal hydrides and other materials in a hydrogen economy. In addition, the used method can be applied to simultaneously study the hydrogenation kinetics in thin-film materials for a wide set of experimental conditions.@en