The recent market introduction of hydrogen fuel cell cars and the prospect of a hydrogen economy have drastically accelerated the need for safe and accurate detection of hydrogen. In this Letter, we investigate the use of arrays of nanofabricated Pd-Au alloy nanoparticles as plasmonic optical hydrogen sensors. By increasing the amount of Au in the alloy nanoparticles up to 25 atom %, we are able to suppress the hysteresis between hydrogen absorption and desorption, thereby increasing the sensor accuracy to below 5% throughout the investigated 1 mbar to 1 bar hydrogen pressure range. Furthermore, we observe an 8-fold absolute sensitivity enhancement at low hydrogen pressures compared to sensors made of pure Pd, and an improved sensor response time to below one second within the 0-40 mbar pressure range, that is, below the flammability limit, by engineering the nanoparticle size.

Hematite (α-Fe 2 O 3 ) has emerged as a promising material for photoelectrochemical (PEC) water splitting thanks to its abundance, stability in aqueous environment, favorable optical bandgap and position of the electronic valence band. Nevertheless, its performance as photoanode is considerably lower than what is theoretically achievable. In particular, the high electrochemical potential usually needed to initiate water oxidation is detrimental to the prospect of using hematite for practical devices. In this review we elucidate the appealing, as well as the challenging, aspects of using hematite for PEC water splitting and focus on the recent efforts towards lowering the onset potential of water oxidation. We examine and rationalize several strategies pursued to achieve this goal involving manipulation of the hematite/electrolyte interface, as well as, improving relevant properties of hematite itself.

Mixing different elements at the nanoscale to obtain alloy nanostructures with fine-tuned physical and chemical properties offers appealing opportunities for nanotechnology and nanoscience. However, despite widespread successful application of alloy nanoparticles made by colloidal synthesis in heterogeneous catalysis, nanoalloy systems have been used very rarely in solid-state devices and nanoplasmonics-related applications. One reason is that such applications require integration in arrays on a surface with compelling demands on nanoparticle arrangement, uniformity in surface coverage, and optimization of the surface density. These cannot be fulfilled even using state-of-the-art self-assembly strategies of colloids. As a solution, we present here a generic bottom-up nanolithography-compatible fabrication approach for large-area arrays of alloy nanoparticles on surfaces. To illustrate the concept, we focus on Au-based binary and ternary alloy systems with Ag, Cu, and Pd, due to their high relevance for nanoplasmonics and complete miscibility, and characterize their optical properties. Moreover, as an example for the relevance of the obtained materials for integration in devices, we demonstrate the superior and hysteresis-free plasmonic hydrogen-sensing performance of the AuPd alloy nanoparticle system.

Hematite (α-Fe2 O3 ) is an extensively investigated semiconductor for photoelectrochemical (PEC) water splitting. The nature and role of surface states on the oxygen evolution reaction (OER) remain however elusive. First-principles calculations were used to investigate surface states on hematite under photoelectrochemical conditions. The density of states for two relevant hematite terminations was calculated, and in both cases the presence and the role of surface states was rationalized. Calculations also predicted a Nerstian dependence on the OER onset potential on pH, which was to a very good extent confirmed by PEC measurements on hematite model photoanodes. Impedance spectroscopy characterization confirmed that the OER takes place via the same surface states irrespective of pH. These results provide a framework for a deeper understanding of the OER when it takes place via surface states.