Size-Dependent Kinetics of Hydriding and Dehydriding of Pd Nanoparticles

Using a new indirect nanoplasmonic sensing method with subsecond resolution, we have studied hydriding and dehydriding kinetics of Pd nanoparticles in the size range 1.8-5.4 nm. Strong particle-size effects are observed. The scaling of the hydriding and dehydriding time scales satisfies power and power-exponential laws. The former (with an exponent of 2.9) is in perfect agreement with Monte Carlo simulations of diffusion-controlled hydriding kinetics. The latter is explained by the effect of surface tension on hydrogen desorption from the surface layer. The approach is generalizable to other reactant-nanoparticle systems

Intrinsic Fano Interference of Localized Plasmons in Pd Nanoparticles

Palladium (Pd) nanoparticles exhibit broad optical resonances that have been assigned to so-called localized surface plasmons (LSPs). The resonance's energy varies with particle shape in a similar fashion as is well known for LSPs in gold and silver nanoparticles, but the line-shape is always anomalously asymmetric. We here show that this effect is due to an intrinsic Fano interference caused by the coupling between the plasmon response and a structureless background originating from interband transitions. The conclusions are supported by experimental and numerical simulation data of Pd particles of different shape and phenomenologically analyzed in terms of the point dipole polarizability of spheroids. The latter analysis indicates that the degree of Fano asymmetry is simply linearly proportional to the imaginary part of the interband contribution to the metal dielectric function

Oscillatory Optical Response of an Amorphous Two-Dimensional Array of Gold Nanoparticles

The optical response of metallic nanoparticle arrays is dominated by localized surface plasmon excitations and is the sum of individual particle contributions modified by interparticle coupling that depends on specific array geometry. We demonstrate a so far unexplored distinct oscillatory behavior of the plasmon peak position, full width at half maximum, and extinction efficiency in large area amorphous arrays of Au nanodisks, which depend on the minimum particle center-to-center distance in the array. Amorphous arrays exhibit short-range order and are completely random at long distances. In our theoretical analysis we introduce a film of dipoles approach, within the framework of the coupled dipole approximation, which describes the array as an average particle surrounded by a continuum of dipoles with surface densities determined by the pair correlation function of the array

Thermodynamics of hydride formation and decomposition in supported sub-10 nm Pd nanoparticles of different sizes

Hydrogen storage properties of supported Pd nanoparticles with average sizes in the range 2.7-7.6 nm were studied using indirect nanoplasmonic sensing. For each particle size, a series of isotherms was measured and, through Van't Hoff analysis, the changes in enthalpy upon hydride formation/decomposition were determined. Contrary to the expected decrease of the enthalpy, due to increasing importance of surface tension in smaller particles, we observe a very weak size dependence in the size range under consideration. We attribute this to a compensation effect due to an increased fraction of hydrogen atoms occupying energetically favorable subsurface sites in smaller nanoparticles

Dynamic Depolarization in Plasmonic Metal Nanoparticles

At very low photon energies most metals have a very large and negative dielectric function. For the response of a metal nanoparticle to an external field in this limit, this means that the particular choice of metal does not matter and the localized surface plasmon energy mainly depends on the shape and size of the particle. Here, we present a theoretical framework to describe this situation and unearth the interplay between the depolarization factor of the problem at hand and the dielectric function of the particle. Available experimental results compare favorably with our theoretical framework