Ni-CeO2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO2 at temperatures as low as 300 K, generating CHx and COx species on the surface of the catalyst. Strong metal-support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) to only 0.15 eV on Ni/CeO2-x (111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CHx or C species are detected in the C 1s XPS region. The reforming of methane proceeds in a clean and efficient way.

The growth of bilayer and multilayer graphene on copper foils was studied by isotopic labeling of the methane precursor. Isotope-labeled graphene films were characterized by micro-Raman mapping and time-of-flight secondary ion mass spectrometry. Our investigation shows that during growth at high temperature, the adlayers formed simultaneously and beneath the top, continuous layer of graphene and the Cu substrate. Additionally, the adlayers share the same nucleation center and all adlayers nucleating in one place have the same edge termination. These results suggest that adlayer growth proceeds by catalytic decomposition of methane (or CH(x), x < 4) trapped in a "nano-chemical vapor deposition" chamber between the first layer and the substrate. On the basis of these results, submillimeter bilayer graphene was synthesized by applying a much lower growth rate.

Pt nanoparticles grown on fully oxidized and partially reduced CeO x (111) thin films have been studied by scanning tunneling microscopy and X-ray photoelectron spectroscopy to understand the effect of redox properties and nanostructures of ceria supports on the growth of Pt. Deposition of 0.2 ML of Pt on CeO2 at 300 K produces two atomic layer high nanoparticles, while on reduced ceria films Pt favors the growth of smaller particles of one−two layer thick with a larger particle density. With the increase of Pt coverage, Pt particles on CeO2 grow in size while the Pt particle density significantly increases on the reduced ceria. Heating the surface to higher temperatures causes the Pt particle agglomeration, but Pt particles sinter less on the reduced ceria compared to those on the fully oxidized ceria. New particle structures are formed on reduced ceria as a result of heating which are suggested due to the encapsulation of Pt particles by ceria. In addition to the structural changes of the Pt particles, modifications of electronic properties of both ceria and Pt were observed upon Pt deposition as well as after heating. Our combined scanning tunneling microscopy and X-ray photoelectron spectroscopy studies suggest a complex growth behavior of Pt on ceria and a strong interaction between the Pt and the ceria support.

We present an extensive experimental study of the conditions under which Cu forms encapsulated islands under the top surface layers of graphite, as a result of physical vapor deposition of Cu on argon-ionbombarded graphite. When the substrate is held at 800 K during deposition, conditions are optimal for formation of encapsulated multilayer Cu islands. Deposition temperatures below 600 K favor adsorbed Cu clusters, while deposition temperatures above 800 K favor a different type of feature that is probably a singlelayer intercalated Cu island. The multilayer Cu islands are characterized with respect to size and shape, thickness and continuity of the graphitic overlayer, relationship to graphite steps, and stability in air. The experimental techniques are scanning tunneling microscopy and X-ray photoelectron spectroscopy. We also present an extensive study using density functional theory to compare stabilities of a wide variety of configurations of Cu atoms, Cu clusters, and Cu layers on/under the graphite surface. The only configuration that is significantly more stable under the graphite surface than on top of it, is a single Cu atom. This analysis leads us to conclude that formation of encapsulated Cu islands is kinetically driven, rather than thermodynamically driven.