Thermal evolution of the submonolayer near-surface alloy of ZnPd on Pd(111).

We have performed a high-resolution synchrotron radiation photoelectron spectroscopy study of the initial growth stages of the ZnPd near-surface alloy on Pd(111), complemented by scanning tunnelling microscopy data. We show that the chemical environment for surfaces containing less than half of one monolayer of Zn is chemically distinct from subsequent layers. Surfaces where the deposition is performed at room temperature contain ZnPd islands surrounded by a substrate with dilute Zn substitutions.

Transmetallation as an effective strategy for the preparation of bimetallic CoPd and CuPd nanoparticles.

The preparation of palladium alloy nanoparticles is of great interest for many applications, especially in catalysis. Starting from presynthesized nanoparticles of a less noble metal, a transmetallation reaction involving a redox process at the nanoparticle surface can be exploited to modify the nanoparticle composition and crystalline phase. As an example, monodispersed ε-cobalt and face-centered cubic copper nanoparticles were synthesized in organic solvents at high temperature and the as-formed nanoparticles were reacted with palladium(ii) hexafluoroacetylacetonate resulting in the formation of alloyed nanoparticles whose composition closely follows the reactant ratio.

Surface structure of Pd(111) with less than half a monolayer of Zn.

We have characterized the structural properties of submonolayer amounts of Zn on Pd(111) using scanning tunneling microscopy (STM) and spot-profile analysis low energy electron diffraction (SPA-LEED). Following room temperature deposition of ≈0.06 monolayers (ML) Zn onto Pd(111), we observe the substitution of Zn for Pd in the surface layer.

Hollow ruthenium nanoparticles with small dimensions derived from Ni@Ru core@shell structure: synthesis and enhanced catalytic dehydrogenation of ammonia borane.

Hollow Ru nanoparticles with ~14 nm diameter and ~2 nm shell thickness are reported for the first time, by removal of Ni from the delicately designed Ni@Ru core@shell NPs. Such hollow Ru NPs exhibit enhanced catalytic activity in the dehydrogenation of ammonia borane with respect to solid ones.

Synthesis of Ni-Ru alloy nanoparticles and their high catalytic activity in dehydrogenation of ammonia borane.

We report the synthesis and characterization of new Ni(x)Ru(1-x) (x = 0.56-0.74) alloy nanoparticles (NPs) and their catalytic activity for hydrogen release in the ammonia borane hydrolysis process.

Bifunctional catalytic/magnetic Ni@Ru core-shell nanoparticles.

Core-shell structured Ni@Ru bimetallic nanoparticles are demonstrated as a bifunctional nanoplatform system for the hydrolysis reaction of ammonia-borane and also for magnetic separation.

Core level shifts of undercoordinated Pt atoms.

We present the results of high-energy resolution core level photoelectron spectroscopy experiments paralleled by density functional theory calculations to investigate the electronic structure of highly undercoordinated Pt atoms adsorbed on Pt(111) and its correlation with chemical activity. Pt4f(7/2) core level binding energies corresponding to atoms in different configurations are shown to be very sensitive not only to the local atomic coordination number but also to the interatomic bond lengths. Our results are rationalized by introducing an indicator, the effective coordination, which includes both contributions.

Comparative study of water dissociation on Rh(111) and Ni(111) studied with first principles calculations.

The dissociation and formation of water on the Rh(111) and Ni(111) surfaces have been studied using density functional theory with generalized gradient approximation and ultrasoft pseudopotentials. Calculations have been performed on 2x2 surface unit cells, corresponding to coverages of 0.25 ML, with spot checks on 3x3 surface unit cells (0.

Ab initio simulation of carbon clustering on an Ni(111) surface: a model of the poisoning of nickel-based catalysts.

In this work, we studied the poisoning of a nickel surface due to carbon. Performing ab initio simulations, within the framework of density functional theory, we computed the surface energy of the nickel (111) surface as a function of carbon coverage. On the basis of these results, we can assert that the stable state of the nickel/carbon surface is either a clean nickel surface or a fully carbon-covered nickel surface, which has a graphitic configuration.

Water production reaction on Rh110.

By means of scanning tunneling microscopy and density functional theory calculations, we studied the water formation reaction on the Rh(110) surface when exposing the (2 x 1)p2mg-O structure to molecular hydrogen, characterizing each of the structures that form on the surface during the reaction. First the reaction propagates on the surface as a wave front, removing half of the initial oxygen atoms. The remaining 0.

Electron localization determines defect formation on ceria substrates.

The high performance of ceria (CeO2) as an oxygen buffer and active support for noble metals in catalysis relies on an efficient supply of lattice oxygen at reaction sites governed by oxygen vacancy formation. We used high-resolution scanning tunneling microscopy and density functional calculations to unravel the local structure of surface and subsurface oxygen vacancies on the (111) surface. Electrons left behind by released oxygen localize on cerium ions.

Structural and kinetic effects on a simple catalytic reaction: oxygen reduction on Ni(110).

Oxygen hydrogenation at 100 K by gas phase atomic hydrogen on Ni(110) has been studied under ultrahigh vacuum conditions by temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS). Formation of adsorbed water and hydroxyl species was observed and characterized. The coverage of the reaction products was monitored as a function of both temperature and initial oxygen precoverage.

Unexpected behavior of the surface composition of PtRh alloys during chemical reaction.

The changes in the surface composition of a Pt(50)Rh(50)(100) alloy due to an ongoing 2H(2) + O(2)-->2H(2)O chemical reaction have been studied in situ. Exploiting the high-energy resolution and surface sensitivity of synchrotron radiation core-level spectroscopy it was possible to monitor the population of the two transitions metals atoms at the gas-surface interface. Sequences of fast high-resolution core-level spectra of the Rh3d(5/2), Pt4f(7/2), and O1s core levels showed a continuous exchange of atoms between the first and subsurface layers.

Two-step reaction on a strained, nanoscale segmented surface.

By means of scanning tunneling microscopy and density functional theory calculations we demonstrate that on the Rh(110)-(10 x 2)-O surface, a prototypical multiphase surface of an oxidized transition metal model catalyst, water formation upon H2 exposure is a two-step reaction, with each step requiring special active sites. The 1st step initiates at (2 x 1)p2mg-O defect islands in the (10 x 2) structure and propagates across the surface as a reaction front, removing half of the adsorbed oxygen. The oxygen decorated Rh ridges of the (10 x 2) structure lose their tensile strain upon this reduction step, whereby nanoscale patches of clean Rh become exposed and act as special reaction sites in the 2nd reaction step, which therefore initiates homogeneously over the entire surface.

Ethanol decomposition: C--C cleavage selectivity on Rh(111).

Ethanol adsorption, desorption and decomposition on Rh(111) have been studied by X-ray photoelectron spectroscopy and tem-perature-programmed desorption experiments. The evolution of the C is and O is core level spectra was monitored as a function of ethanol exposure and surface temperature. Ethanol adsorption at 90 K results in two nonequivalent ethanol-adsorbed species at low surface coverage, while a third species--related to multilayer formation--appears after longer exposures.

Spectroscopic link between adsorption site occupation and local surface chemical reactivity.

In this Letter we show that sequences of adsorbate-induced shifts of surface core level (SCL) x-ray photoelectron spectra contain profound information on surface changes of electronic structure and reactivity. Energy shifts and intensity changes of time-lapsed spectral components follow simple rules, from which adsorption sites are directly determined. Theoretical calculations rationalize the results for transition metal surfaces in terms of the energy shift of the d-band center of mass and this proves that adsorbate-induced SCL shifts provide a spectroscopic measure of local surface reactivity.

Atomic hydrogen interaction with Ru(1010).

The interaction of atomic hydrogen with clean and deuterium precovered Ru(1010) was studied by means of temperature-programmed desorption (TPD) spectroscopy. Compared to molecular hydrogen experiments, after exposure of the clean surface to gas-phase atomic hydrogen at 90 K, two additional peaks grow in the desorption spectra at 115 and 150 K. The surface saturation coverage, determined by equilibrium between abstraction and adsorption reactions, is 2.

Distinct reaction mechanisms in the catalytic oxidation of carbon monoxide on Rh(110): scanning tunneling microscopy and density functional theory studies.

By means of scanning tunneling microscopy measurements and density functional theory calculations, we identify the reaction mechanism for the oxidation of carbon monoxide to carbon dioxide on the Rh(110) surface at 160 K, which appears to be completely different than the one active at room temperature. The reasons for these different behaviors are determined. Our results demonstrate that even for a very simple catalytic reaction, the microscopic mechanism can dramatically change with temperature, following pathways that differ for nucleation sites and surface propagation and involve different surface moieties.