Interface Effects in the Stability of 2D Silica, Silicide, and Silicene on Pt(111) and Rh(111).

Ultrathin two-dimensional silica films have been suggested as highly defined conductive models for fundamental studies on silica-supported catalyst particles. Key requirements in this context are closed silica films that isolate the gas phase from the underlying metal substrate and stability under reaction conditions. Here, we present silica bilayer films grown on Pt(111) and Rh(111) and characterize them by scanning tunneling microscopy and X-ray photoelectron spectroscopy. We provide the first report of silica bilayer films on Rh(111) and have further successfully prepared fully closed films on Pt(111). Interestingly, surface and interface silicide phases play a decisive role in both cases: On platinum, closed films can be stabilized only when silicon is deposited in excess, which results in an interfacial silicide or silicate layer. We show that these silica films can also be grown directly from a surface silicide phase. In the case of rhodium, the silica phase is less stable and can be reduced to a silicide in reductive environments. Though similar in appearance to the "silicene" phases that have been controversially discussed on Ag(111), we conclude that an interpretation of the phase as a surface silicide is more consistent with our data. Finally, we show that the silica film on platinum is stable in 0.8 mbar CO but unstable at elevated temperatures. We thus conclude that these systems are only suitable as model catalyst supports to a limited extent.

On-Surface Carbon Nitride Growth from Polymerization of 2,5,8-Triazido-s-heptazine.

Carbon nitrides have recently come into focus for photo- and thermal catalysis, both as support materials for metal nanoparticles as well as photocatalysts themselves. While many approaches for the synthesis of three-dimensional carbon nitride materials are available, only top-down approaches by exfoliation of powders lead to thin-film flakes of this inherently two-dimensional material. Here, we describe an in situ on-surface synthesis of monolayer 2D carbon nitride films as a first step toward precise combination with other 2D materials. Starting with a single monomer precursor, we show that 2,5,8-triazido-s-heptazine can be evaporated intact, deposited on a single crystalline Au(111) or graphite support, and activated via azide decomposition and subsequent coupling to form a covalent polyheptazine network. We demonstrate that the activation can occur in three pathways, via electrons (X-ray illumination), via photons (UV illumination), and thermally. Our work paves the way to coat materials with extended carbon nitride networks that are, as we show, stable under ambient conditions.

Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe3O4(001) by SMSI.

The metastability of supported metal nanoparticles limits their application in heterogeneous catalysis at elevated temperatures due to their tendency to sinter. One strategy to overcome these thermodynamic limits on reducible oxide supports is encapsulation via strong metal-support interaction (SMSI). While annealing-induced encapsulation is a well-explored phenomenon for extended nanoparticles, it is as yet unknown whether the same mechanisms hold for subnanometer clusters, where concomitant sintering and alloying might play a significant role. In this article, we explore the encapsulation and stability of size-selected Pt5, Pt10, and Pt19 clusters deposited on Fe3O4(001). In a multimodal approach using temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM), we demonstrate that SMSI indeed leads to the formation of a defective, FeO-like conglomerate encapsulating the clusters. By stepwise annealing up to 1023 K, we observe the succession of encapsulation, cluster coalescence, and Ostwald ripening, resulting in square-shaped crystalline Pt particles, independent of the initial cluster size. The respective sintering onset temperatures scale with the cluster footprint and thus size. Remarkably, while small encapsulated clusters can still diffuse as a whole, atom detachment and thus Ostwald ripening are successfully suppressed up to 823 K, i.e., 200 K above the Hüttig temperature that indicates the thermodynamic stability limit.

Formation of active sites on transition metals through reaction-driven migration of surface atoms.

Adopting low-index single-crystal surfaces as models for metal nanoparticle catalysts has been questioned by the experimental findings of adsorbate-induced formation of subnanometer clusters on several single-crystal surfaces. We used density functional theory calculations to elucidate the conditions that lead to cluster formation and show how adatom formation energies enable efficient screening of the conditions required for adsorbate-induced cluster formation. We studied a combination of eight face-centered cubic transition metals and 18 common surface intermediates and identified systems relevant to catalytic reactions, such as carbon monoxide (CO) oxidation and ammonia (NH3) oxidation. We used kinetic Monte Carlo simulations to elucidate the CO-induced cluster formation process on a copper surface. Scanning tunneling microscopy of CO on a nickel (111) surface that contains steps and dislocations points to the structure sensitivity of this phenomenon. Metal-metal bond breaking that leads to the evolution of catalyst structures under realistic reaction conditions occurs much more broadly than previously thought.

Nanoscale patterning at the Si/SiO2/graphene interface by focused He+ beam.

We have studied the capability of He+ focused ion beam (He+-FIB) patterning to fabricate defect arrays on the Si/SiO2/Graphene interface using a combination of atomic force microscopy (AFM) and Raman imaging to probe damage zones. In general, an amorphized 'blister' region of cylindrical symmetry results upon exposing the surface to the stationary focused He+ beam. The topography of the amorphized region depends strongly on the ion dose, DS , (ranging from 103 to 107ions/spot) with craters and holes observed at higher doses. Furthermore, the surface morphology depends on the distance between adjacent irradiated spots, LS . Increasing the dose leads to (enhanced) subsurface amorphization and a local height increase relative to the unexposed regions. At the highest areal ion dose, the average height of a patterned area also increases as ∼1/LS . Correspondingly, in optical micrographs, the µm2-sized patterned surface regions change appearance. These phenomena can be explained by implantation of the He+ ions into the subsurface layers, formation of helium nanobubbles, expansion and modification of the dielectric constant of the patterned material. The corresponding modifications of the terminating graphene monolayer have been monitored by micro Raman imaging. At low ion doses, DS , the graphene becomes modified by carbon atom defects which perturb the 2D lattice (as indicated by increasing D/G Raman mode ratio). Additional x-ray photoionization spectroscopy (XPS) measurements allow us to infer that for moderate ion doses, scattering of He+ ions by the subsurface results in the oxidation of the graphene network. For largest doses and smallest LS values, the He+ beam activates extensive Si/SiO2/C bond rearrangement and a multicomponent material possibly comprising SiC and silicon oxycarbides, SiOC, is observed. We also infer parameter ranges for He+-FIB patterning defect arrays of potential use for pinning transition metal nanoparticles in model studies of heterogeneous catalysis.

Order-disorder phase transition of the subsurface cation vacancy reconstruction on Fe3O4(001).

We present surface X-ray diffraction and fast scanning tunneling microscopy results to elucidate the nature of the surface phase transition on magnetite (001) from a reconstructed to a non-reconstructed surface around 720 K. In situ surface X-ray diffraction at a temperature above the phase transition, at which long-range order is lost, gives evidence that the subsurface cation vacancy reconstruction still exists as a local structural motif, in line with the characteristics of a 2D second-order phase transition. Fast scanning tunneling microscopy results across the phase transition underpin the hypothesis that the reconstruction lifting is initiated by surplus Fe ions occupying subsurface octahedral vacancies. The reversible near-surface iron enrichment and reduction of the surface to stoichiometric composition is further confirmed by in situ low-energy ion scattering, as well as ultraviolet and X-ray photoemission results.

The new FAST module: A portable and transparent add-on module for time-resolved investigations with commercial scanning probe microscopes.

Time resolution is one of the most severe limitations of scanning probe microscopies (SPMs), since the typical image acquisition times are in the order of several seconds or even few minutes. As a consequence, the characterization of dynamical processes occurring at surfaces (e.g. surface diffusion, film growth, self-assembly and chemical reactions) cannot be thoroughly addressed by conventional SPMs. To overcome this limitation, several years ago we developed a first prototype of the FAST module, an add-on instrument capable of driving a commercial scanning tunneling microscope (STM) at and beyond video rate frequencies. Here we report on a fully redesigned version of the FAST module, featuring improved performance and user experience, which can be used both with STMs and atomic force microscopes (AFMs), and offers additional capabilities such as an atom tracking mode. All the new features of the FAST module, including portability between different commercial instruments, are described in detail and practically demonstrated.

Scanning Tunneling Microscopy Study of the Structure and Interaction between Carbon Monoxide and Hydrogen on the Ru(0001) Surface.

We use scanning tunneling microscopy (STM) to investigate the spatial arrangement of carbon monoxide (CO) and hydrogen (H) coadsorbed on a model catalyst surface, Ru(0001). We find that at cryogenic temperatures, CO forms small triangular islands of up to 21 molecules with hydrogen segregated outside of the islands. Furthermore, whereas for small island sizes (3-6 CO molecules) the molecules adsorb at hcp sites, a registry shift toward top sites occurs for larger islands (10-21 CO molecules). To characterize the CO structures better and to help interpret the data, we carried out density functional theory (DFT) calculations of the structure and simulations of the STM images, which reveal a delicate interplay between the repulsions of the different species.

Dynamic restructuring drives catalytic activity on nanoporous gold-silver alloy catalysts.

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver-gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changes occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.

Recycling of CO2: Probing the Chemical State of the Ni(111) Surface during the Methanation Reaction with Ambient-Pressure X-Ray Photoelectron Spectroscopy.

Using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), we studied the adsorption and reactions of CO2 and CO2 + H2 on the Ni(111) surface to identify the surface chemical state and the nature of the adsorbed species during the methanation reaction. In 200 mTorr CO2, we found that NiO is formed from CO2 dissociation into CO and atomic oxygen. Additionally, carbonate (CO32-) is present on the surface from further reaction of CO2 with NiO. The addition of H2 into the reaction environment leads to reduction of NiO and the disappearance of CO32-. At temperatures >160 °C, CO adsorbed on hollow sites, and atomic carbon and OH species are present on the surface. We conclude that the methanation reaction proceeds via dissociation of CO2, followed by reduction of CO to atomic carbon and its hydrogenation to methane.

Growth and Structure of the First Layers of Ice on Ru(0001) and Pt(111).

Scanning tunneling microscopy was used to probe the structure and growth of the first few layers of water on Ru(0001) and Pt(111) at the molecular level. The surface-bound first layer is composed of a mixture of water molecules forming hexagonal structures, both in registry and out-of-registry with the substrate atoms. The hexagons are connected by pentagonal and heptagonal units. At temperatures below 140 K, this layer structure gives rise to the growth of metastable amorphous structures in the second and higher layers. We found that in the transition from amorphous to crystalline ice the structure of the original bottom layer changes to one in perfect local registry with the hexagonal surfaces of Ru(0001) and Pt(111). We further discovered structural defects in the form of extended one-dimensional lines of five- and eight-membered rings that are domain boundaries and stacking faults in the growing ice layers, which lead to the formation of metastable cubic ice.

Coupling between diffusion and orientation of pentacene molecules on an organic surface.

The realization of efficient organic electronic devices requires the controlled preparation of molecular thin films and heterostructures. As top-down structuring methods such as lithography cannot be applied to van der Waals bound materials, surface diffusion becomes a structure-determining factor that requires microscopic understanding. Scanning probe techniques provide atomic resolution, but are limited to observations of slow movements, and therefore constrained to low temperatures. In contrast, the helium-3 spin-echo (HeSE) technique achieves spatial and time resolution on the nm and ps scale, respectively, thus enabling measurements at elevated temperatures. Here we use HeSE to unveil the intricate motion of pentacene admolecules diffusing on a chemisorbed monolayer of pentacene on Cu(110) that serves as a stable, well-ordered organic model surface. We find that pentacene moves along rails parallel and perpendicular to the surface molecules. The experimental data are explained by admolecule rotation that enables a switching between diffusion directions, which extends our molecular level understanding of diffusion in complex organic systems.

Vibrational lifetimes and friction in adsorbate motion determined from quasi-elastic scattering.

The vibrational excitation of molecules adsorbed on a surface is typically probed by spectroscopic techniques such as infrared or Raman spectroscopy. In the present article we demonstrate an alternative method to determine vibrational lifetimes of adsorbate molecules using quasi-elastic helium atom scattering (QHAS). As a probe of diffusive motion of molecules on surfaces QHAS is well established. Here, we demonstrate that QHAS can also be used to probe the vibrational lifetime of a molecule in its adsorption well. Measurements of cyclopentadienyl, C5H5, on Cu(111) allow us to distinguish two substrate phonon modes as well as two molecular vibrational modes, perpendicular and parallel to the surface. We further find that the dephasing of the vibrational motion corresponds to the friction determined in previous diffusion measurements.

Jumping, Rotating, and Flapping: The Atomic-Scale Motion of Thiophene on Cu(111).

Self-assembled monolayers of sulfur-containing heterocycles and linear oligomers containing thiophene groups have been widely employed in organic electronic applications. Here, we investigate the dynamics of isolated thiophene molecules on Cu(111) by combining helium spin-echo (HeSE) spectroscopy with density functional theory calculations. We show that the thiophene/Cu(111) system displays a rich array of aperiodic dynamical phenomena that include jump diffusion between adjacent atop sites over a 59-62 meV barrier and activated rotation around a sulfur-copper anchor, two processes that have been observed previously for related systems. In addition, we present experimental evidence for a new, weakly activated process, the flapping of the molecular ring. Repulsive inter-adsorbate interactions and an exceptionally high friction coefficient of 5 ± 2 ps(-1) are also observed. These experiments demonstrate the versatility of the HeSE technique, and the quantitative information extracted in a detailed analysis provides an ideal benchmark for state-of-the-art theoretical techniques including nonlocal adsorbate-substrate interactions.