This study presents the synthesis of monodisperse Pd nanoparticles (NPs) stabilized by sodium oleate (NaOL) and hexadecyltrimethylammonium chloride (CTAC). The synthesis was conducted without traditional reductants and Pd-precursors are reduced by NaOL. It was confirmed that the alkyl double bond in NaOL is not the only explanation for the reduction of Pd-precursors since Pd NPs could be synthesized with CTAC and the saturated fatty acid sodium stearate (NaST). A quantitative evaluation of the reduction kinetics using UV-Vis spectroscopy shows that Pd NPs synthesized with both stabilizer combinations follow pseudo first-order reaction kinetics, where NaOL provides a faster and more effective reduction of Pd-precursors. The colloidal stabilization of the NP surface by CTAC and NaOL is confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) analysis.

Hydrogen (H2) sensors that can be produced en masse with cost-effective manufacturing tools are critical for enabling safety in the emerging hydrogen economy. The use of melt-processed nanocomposites in this context would allow the combination of the advantages of plasmonic hydrogen detection with polymer technology; an approach which is held back by the slow diffusion of H2 through the polymer matrix. Here, we show that the use of an amorphous fluorinated polymer, compounded with colloidal Pd nanoparticles prepared by highly scalable continuous flow synthesis, results in nanocomposites that display a high H2 diffusion coefficient in the order of 10–5 cm2 s–1. As a result, plasmonic optical hydrogen detection with melt-pressed fluorinated polymer nanocomposites is no longer limited by the diffusion of the H2 analyte to the Pd nanoparticle transducer elements, despite a thickness of up to 100 μm, thereby enabling response times as short as 2.5 s at 100 mbar (≡10 vol. %) H2. Evidently, plasmonic sensors with a fast response time can be fabricated with thick, melt-processed nanocomposites, which paves the way for a new generation of robust H2 sensors.

Nanoplasmonic hydrogen sensors are predicted to play a key role in safety systems of the emerging hydrogen economy. Pd nanoparticles are the active material of choice for sensor prototype development due to their ability to form a hydride at ambient conditions, which creates the optical contrast. Here, we introduce plasmonic hydrogen sensors made from a thermoplastic nanocomposite material, that is, a bulk material that can be molded with standard plastic processing techniques, such as extrusion and three-dimensional (3D) printing, while at the same time being functionalized at the nanoscale. Specifically, our plasmonic plastic is composed of hydrogen-sensitive and plasmonically active Pd nanocubes mixed with a poly(methyl methacrylate) matrix, and we optimize it by characterization from the atomic to the macroscopic level. We demonstrate melt-processed deactivation-resistant plasmonic hydrogen sensors, which retain full functionality even after 50 weeks. From a wider perspective, we advertise plasmonic plastic nanocomposite materials for application in a multitude of active plasmonic technologies since they provide efficient scalable processing and almost endless functional material design opportunities via tailored polymer–colloidal nanocrystal combinations.

Nanoparticle dimers composed of different metals or metal oxides, as well as different shapes and sizes, are of wide interest for applications ranging from nanoplasmonic sensing to nanooptics to biomedical engineering. Shaped nanoparticles, like triangles and nanorods, can be particularly useful in applications due to the strong localized plasmonic hot-spot that forms at the tips or corners. By placing catalytic, but traditionally weakly- or non-plasmonic nanoparticles, such as metal oxides and metals like palladium, in these hot-spots, an enhanced function for sensing, photocatalysis or optical use is predicted. Here, we present an electrostatic colloidal assembly strategy for nanoparticles, incorporating different sizes, shapes and metal or metal oxide compositions into heterodimers with smaller gaps than are achievable using nanofabrication techniques. This versatile method is demonstrated on 14 combinations, including a variety of shaped gold nanoparticles as well as palladium, iron oxide, and titanium oxide nanoparticles. These colloidal nanoparticles are stabilized with traditional surfactants, such as citrate, CTAB, PVP and oleic acid/oleylamines, indicating the wide applicability of our approach. Heterodimers of gold and palladium are further analyzed using cathodoluminescence to demonstrate the tunability of these “plasmonic molecules”. Since systematically altering the absorption and emission of the plasmonic nanoparticles dimers is crucial to extending their functionality, and small gap sizes produce the strongest hot-spots, this method indicates that the electrostatic approach to heterodimer assembly can be useful in creating new nanoparticle dimers for many applications.

Surfactants and stabilizers are always present on the surfaces of colloidal nanocrystals due to their critical function in promoting selective facet growth and since they are essential to prevent aggregate formation in solution. After synthesis, however, the presence of these molecules on the surface of a nanocrystal is problematic because they potentially significantly alter the nature of the interaction with the environment, which is critical for sensor or catalysis applications. Here, we quantitatively scrutinize this effect experimentally for the four most common stabilizers in Pd nanoparticle synthesis: cetyltrimethylammonium bromide (CTAB), tetraoctylammonium bromide (TOAB), cetyltrimethylammonium chloride (CTAC), and poly(vinylpyrrolidone) (PVP). We use the surface-catalyzed hydrogen sorption and hydride formation reaction in Pd as a model system, due to its high relevance for hydrogen sensors. Specifically, we map in detail the (de)hydrogenation kinetics of arrays of nanofabricated Pd nanodisks in the presence of the surfactants and benchmark it with an uncoated Pd reference. As the key results, we find that the cationic surfactants significantly decelerate the (de)hydrogenation surface reaction, with the amplitude of deceleration mediated by the interplay between the halide-ion–Pd surface interaction strength and surfactant surface density. In contrast, a polymeric PVP coating is found to significantly accelerate hydrogen sorption. For the Pd-based hydrogen sensor application, our findings thus provide important insights for the appropriate choice of a surfactant to minimize the negative impact on hydrogen sorption kinetics and thus hydrogen detection response/recovery times. In a wider perspective, our results dramatically show how nanoparticles can attain different properties depending on what types of surfactants and stabilizers are present on their surface and how critical the quantitative understanding of their impact is for a specific application

Optical, and catalytic properties. However, continuous flow synthesis that enables rapid formation of faceted nanoparticles of single or multi-elemental composition is not trivial. We present a continuous flow synthesis route for the synthesis of uniformly sized Pd nanocubes and PdPt core–shell nanoparticles in a single-phase microfluidic reactor, which enables rapid formation of shaped nanoparticles with a reaction time of 3 min. The PdPt core–shell nanoparticles feature a dendritic, high surface area with the Pt shell covering the Pd core, as verified using high-resolution scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. The Pd nanocubes and PdPt core–shell particles are catalytically tested during NO2 reduction in the presence of H2 in a flow pocket reactor. The Pd nanocubes exhibited low-temperature activity (i.e., <136 °C) and poor selectivity performance toward production of N2O or N2, whereas PdPt core–shell nanoparticles showed higher activity and were found to achieve better selectivity during NO2 reduction retaining its basic structure at relatively elevated temperatures, making the PdPt core–shell particles a unique, desirable synergic catalyst material for potential use in NOx abatement processes.