Grain boundaries separate crystallites in solids and influence material properties, as widely documented for bulk materials. In nanomaterials, however, investigations of grain boundaries are very challenging and just beginning. Here, we report the systematic mapping of the role of grain boundaries in the hydrogenation phase transformation in individual Pd nanoparticles. Employing multichannel single-particle plasmonic nanospectroscopy, we observe large variation in particle-specific hydride-formation pressure, which is absent in hydride decomposition. Transmission Kikuchi diffraction suggests direct correlation between length and type of grain boundaries and hydride-formation pressure. This correlation is consistent with tensile lattice strain induced by hydrogen localized near grain boundaries as the dominant factor controlling the phase transition during hydrogen absorption. In contrast, such correlation is absent for hydride decomposition, suggesting a different phase-transition pathway. In a wider context, our experimental setup represents a powerful platform to unravel microstructure–function correlations at the individual-nanoparticle level.
Single particle nanoplasmonic sensing and spectroscopy is a powerful and at the same time relatively easy-to-implement research method that allows monitoring of changes in the structure and properties of metal nanoparticles in real time and with only few restrictions in terms of surrounding medium, temperature and pressure. Consequently, it has been successfully used in materials science applications to, for instance, reveal the impact of size and shape of single metal nanoparticles on the thermodynamics of metal hydride formation and decomposition. In this Perspective, we review and discuss the research efforts that have spurred key advances in the development of single particle nanoplasmonic sensing and spectroscopy as a research tool in materials science. On this background we then assess the prospects and challenges toward its application in single particle catalysis, with the aim to enable operando studies of the relationship between metal nanoparticle structure or oxidation state and catalytic performance.
The ongoing quest to develop single-particle methods for the in situ study of heterogeneous catalysts is driven by the fact that heterogeneity in terms of size, shape, grain structure, and composition is a general feature among nanoparticles in an ensemble. This heterogeneity hampers the generation of a deeper understanding for how these parameters affect catalytic properties. Here we present a solution that in a single benchtop experimental setup combines single-particle plasmonic nanospectroscopy with mass spectrometry for gas phase catalysis under reaction conditions at high temperature. We measure changes in the surface state of polycrystalline platinum model catalyst particles in the 70 nm size range and the corresponding bistable kinetics during the carbon monoxide oxidation reaction via the peak shift of the dark-field scattering spectrum of a closely adjacent plasmonic nanoantenna sensor and compare these changes with the total reaction rate measured by the mass spectrometer from an ensemble of nominally identical particles. We find that the reaction kinetics of simultaneously measured individual Pt model catalysts are dictated by the grain structure and that the superposition of the individual nanoparticle response can account for the significant broadening observed in the corresponding nanoparticle ensemble data. In a wider perspective our work enables in situ plasmonic nanospectroscopy in controlled gas environments at high temperature to investigate the role of the surface state on transition metal catalysts during reaction and of processes such as alloying or surface segregation in situ at the single-nanoparticle level for model catalysts in the few tens to hundreds of nanometer size range.
Grains constitute the building blocks of polycrystalline materials and their boundaries determine bulk physical properties like electrical conductivity, diffusivity and ductility. However, the structure and evolution of grains in nanostructured materials and the role of grain boundaries in reaction or phase transformation kinetics are poorly understood, despite likely importance in catalysis, batteries and hydrogen energy technology applications. Here we report an investigation of the kinetics of (de)hydriding phase transformations in individual Pd nanoparticles. We find dramatic evolution of single particle grain morphology upon cyclic exposure to hydrogen, which we identify as the reason for the observed rapidly slowing sorption kinetics, and as the origin of the observed kinetic compensation effect. These results shed light on the impact of grain growth on kinetic processes occurring inside nanoparticles, and provide mechanistic insight in the observed kinetic compensation effect.
Lithographic method of making nanoarchitectures composed of metal core and oxide/nitride shell decorated with nanoparticles with widely different materials.
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