Morphological Instability of Metallic Surfaces: Adsorbate Induced Nanoscale Faceting

Heterogeneous catalysis is a field of major interest in the surface science and development of new supported model catalysts with a narrow size distribution. The possibility to create narrow size distributions is to use the faceted surface structures as self assembled templates on which metal nanoclusters can grow. In the present study, new aspects of adsorbate induced faceting and nanoscale phenomena on adsorbate-covered metallic surfaces are studied on atomically-rough morphologically unstable metallic fcc (Rh) and hcp (Re) surfaces. Formation of oxygen induced faceting of atomically-rough Rh (210) surface has been studied and characterized by means of LEED, STM and AES. The LEED studies confirm the formation of three sided faceted (nanoscale pyramidal structure) Rh(210) surface when the oxygen covered Rh surface annealed to temperature higher than 550K. The facet orientations of the nanopyramid are characterized as two {731} face and a reconstructed (110) face. The excess oxygen overlayer can be removed from pyramidal faceted Rh(210) surface via catalytic reaction at low temperature using CO oxidation or H2 reaction while preserving the pyramidal structure. The average size of the nanopyramids is observed to be dependent on annealing temperature and vary from 12nm to 21nm. The atomically resolved STM images confirm the LEED observations and also revealed that (110) face of nanopyramids exhibits various reconstructions (1×n, n = 2-4) depending on oxygen coverage. Further, oxygen induced nanoscale faceted Re (12-31) surface has been formed which consist of nano-trenches (two sided ridges) with facets in (11-21) and (01-10) direction. These two- sided faceted Re (12-31) surface is used as a template to grow gold nanostructures. Under controlled growth conditions, the gold induced nanostructures are formed on oxygen induced nano-trenched Re (12-31) surface. It is observed that gold grows in the form of islands on the faceted rhenium substrate i.e. at lower coverages (≥0.8ML), it forms 2D islands whereby for higher coverages 3D islands are formed on top of the nano-ridges. The surfaces morphology of the gold covered faceted Re surface changes drastically on annealing, for the temperature >870 K, gold atoms wet the rhenium template while annealing to higher temperature (˜970K) led to the development of a three sided nanopyramids. On further annealing to higher temperatures (>1100K) cause the complete destruction of the faceted structure. LEED and STM studies revealed that the gold induced three sided nanopyramids consists of two faces of original two sided ridges with (11-20), (01-10) orientation and an additional facet in (12-32) direction. The high resolution STM images revealed that the (12-32) facet of the nanopyramid is fully decorated with single atomic zigzag gold nanochain. These faceted surfaces can be potential template for heterogeneous catalysis and development of new supported model catalysts with a narrow size distribution.