Cerium Oxide Nanoclusters on Graphene/Ru(0001): Intercalation of Oxygen <i>via</i> Spillover

Cerium oxide is an important catalytic material known for its ability to store and release oxygen, and as such, it has been used in a range of applications, both as an active catalyst and as a catalyst support. Using scanning tunneling microscopy and Auger electron spectroscopy, we investigated oxygen interactions with CeO_<i>x</i> nanoclusters on a complete graphene monolayer-covered Ru(0001) surface at elevated temperatures (600–725 K). Under oxidizing conditions (<i>P</i>_O₂ = 1 × 10^–7 Torr), oxygen intercalation under the graphene layer is observed. Time dependent studies demonstrate that the intercalation proceeds <i>via</i> spillover of oxygen from CeO_<i>x</i> nanoclusters through the graphene (Gr) layer onto the Ru(0001) substrate and extends until the Gr layer is completely intercalated. Atomically resolved images further show that oxygen forms a <i>p</i>(2 × 1) structure underneath the Gr monolayer. Temperature dependent studies yield an apparent kinetic barrier for the intercalation of 1.21 eV. This value correlates well with the theoretically determined value for the reduction of small CeO₂ clusters reported previously. At higher temperatures, the intercalation is followed by a slower etching of the intercalated graphene (apparent barrier of 1.60 eV). Vacuum annealing of the intercalated Gr leads to the formation of carbon monoxide, causing etching of the graphene film, demonstrating that the spillover of oxygen is not reversible. In agreement with previous studies, no intercalation is observed on a complete graphene monolayer without CeO_<i>x</i> clusters, even in the presence of a large number of point defects. These studies demonstrate that the easily reducible CeO_<i>x</i> clusters act as intercalation gateways capable of efficiently delivering oxygen underneath the graphene layer

Stability of Iridium Single Atoms on Fe₃O₄(001) in the mbar Pressure Range

Stable single metal adatoms on oxide surfaces are of great interest for future applications in the field of catalysis. We studied iridium single atoms (Ir1) supported on a Fe3O4(001) single crystal, a model system previously only studied in ultra-high vacuum, to explore their behavior upon exposure to several gases in the millibar range (up to 20 mbar) utilizing ambient-pressure X-ray photoelectron spectroscopy. The Ir1 single adatoms appear stable upon exposure to a variety of common gases at room temperature, including oxygen (O2), hydrogen (H2), nitrogen (N2), carbon monoxide (CO), argon (Ar), and water vapor. Changes in the Ir 4f binding energy suggest that Ir1 interacts not only with adsorbed and dissociated molecules but also with water/OH groups and adventitious carbon species deposited inevitably under these pressure conditions. At higher temperatures (473 K), iridium adatom encapsulation takes place in an oxidizing environment (a partial O2 pressure of 0.1 mbar). We attribute this phenomenon to magnetite growth caused by the enhanced diffusion of iron cations near the surface. These findings provide an initial understanding of the behavior of single atoms on metal oxides outside the UHV regime

Formation of Supported Graphene Oxide: Evidence for Enolate Species

Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the atomic oxygen (AO) binding and mobility on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites. We employ scanning tunneling microscopy and density functional theory to map out the chemical identity and stability of prepared AO functionalities in different Gr regions. The AO diffusion is utilized to establish that in the regions that are close to the metal substrate the terminally bonded enolate groups are strongly preferred over bridge-bonded epoxy groups. No oxygen species are observed on the graphene regions that are far from the underlying Ru, indicating their low relative stability. This study provides a clear fundamental basis for understanding the local structural, electronic factors and C–Ru bond strengthening/weakening processes that affect the stability of enolate and epoxy species

Water Adsorption at the Tetrahedral Titania Surface Layer of SrTiO₃(110)-(4 × 1)

The interaction of water with oxide surfaces is of great interest for both fundamental science and applications. We present a combined theoretical (density functional theory (DFT)) and experimental (scanning tunneling microscopy (STM) and photoemission spectroscopy (PES)) study of water interaction with the two-dimensional titania overlayer that terminates the SrTiO₃(110)-(4 × 1) surface and consists of TiO₄ tetrahedra. STM and core-level and valence band PES show that H₂O neither adsorbs nor dissociates on the stoichiometric surface at room temperature, whereas it does dissociate at oxygen vacancies. This is in agreement with DFT calculations, which show that the energy barriers for water dissociation on the stoichiometric and reduced surfaces are 1.7 and 0.9 eV, respectively. We propose that water weakly adsorbs on two-dimensional, tetrahedrally coordinated overlayers

Adsorption of CO on the Fe₃O₄(001) Surface

The interaction of CO with the Fe₃O₄(001)-(√2 × √2)­R45° surface was studied using temperature-programmed desorption (TPD), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS), the latter both under ultrahigh vacuum (UHV) conditions and in CO pressures up to 1 mbar. In general, the CO–Fe₃O₄ interaction is found to be weak. The strongest adsorption occurs at surface defects, leading to small TPD peaks at 115, 130, and 190 K. Desorption from the regular surface occurs in two distinct regimes. For coverages up to two CO molecules per (√2 × √2)­R45° unit cell, the desorption maximum shows a large shift with increasing coverage, from initially 105 to 70 K. For coverages between 2 and 4 molecules per (√2 × √2)­R45° unit cell, a much sharper desorption feature emerges at ∼65 K. Thermodynamic analysis of the TPD data suggests a phase transition from a dilute 2D gas into an ordered overlayer with CO molecules bound to surface Fe³⁺ sites. XPS data acquired at 45 K in UHV are consistent with physisorption. Some carbon-containing species are observed in the near-ambient-pressure XPS experiments at room temperature but are attributed to contamination and/or reaction with CO with water from the residual gas. No evidence was found for surface reduction or carburization by CO molecules

Cluster Nucleation and Growth from a Highly Supersaturated Adatom Phase: Silver on Magnetite

The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)<i>R</i>45°-Fe₃O₄(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)<i>R</i>45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)<i>R</i>45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system

Cluster Nucleation and Growth from a Highly Supersaturated Adatom Phase: Silver on Magnetite

The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)<i>R</i>45°-Fe₃O₄(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)<i>R</i>45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)<i>R</i>45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system