Impact of Surfactants and Stabilizers on Palladium Nanoparticle–Hydrogen Interaction Kinetics: Implications for Hydrogen Sensors

Journal article, 2020

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.