Epitaxy and Shape Heterogeneity of a Nanoparticle Ensemble during Redox Cycles

Abstract

The role of metal−support epitaxy on shape and size heterogeneity of nanoparticles and their response to gas atmospheres is not very well explored. Here we show that an ensemble of Pd nanoparticles, grown on MgO(001) by deposition under ultrahigh vacuum, mostly consists of two distinctly epitaxially oriented particles, each having a different structural response to redox cycles. X-ray reciprocal space patterns were acquired in situ under oxidizing and reducing environments. Each type of nanoparticle has a truncated octahedral shape, whereby the majority grows with a cube-oncube epitaxy on the substrate. Less frequently occurring and larger particles have their principal crystal axes rotated ±3.7°with respect to the substrate's. Upon oxidation, the top (001) facets of both types of particles shrink. The relative change of the rotated particles' top facets is much more pronounced. This finding indicates that a larger mass transfer is involved for the rotated particles and that a larger portion of high-index facets forms. On the main facets of the cube-on-cube particles, the oxidation process results in a considerable strain, as concluded from the evolution to largely asymmetric facet scattering signals. The shape and strain responses are reversible upon reduction, either by annealing to 973 K in vacuum or by reducing with hydrogen. The presented results are important for unraveling different elements of heterogeneity and their effect on the performance of real polycrystalline catalysts. It is shown that a correlation can exist between the particle-support epitaxy and redox-cycling-induced shape changes.

Transient heating of Pd nanoparticles studied by x-ray diffraction with time of arrival photon detection

“…Even though there is a large lattice mismatch of 7.3%, it has been previously observed that the epitaxial relationship between Pd and MgO involves a coincidence-site-lattice of the first layers of Pd atoms and the MgO(100). 6 This effect reduces the strain, as would arise from expanding the Pd lattice to match that of MgO. Considering these aspects, it is assumed free lattice expansion of the nanoparticles like that of a single crystal was observed.…”