Cristina Africh

In Situ Observations of the Atomistic Mechanisms of Ni Catalyzed Low Temperature Graphene Growth

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.

Activation of Cu(111) surface by decomposition into nanoclusters driven by CO adsorption

Nanoclusters just by adding CO The most closely packed surfaces of transition metals are usually stable under vacuum, but during catalytic reactions, energetic changes that result from adsorbing molecules could change the surface structure. Eren et al. present an extreme example for carbon monoxide (CO) adsorption on the (111) surface of copper at very low partial pressures. The surface decomposed into small nanoclusters (most containing 3 or 19 atoms). The surface was more reactive than the original and, for example, could dissociate adsorbed water at room temperature. Science, this issue p. 475 The Cu(111) surface decomposes into nanoclusters under CO at pressures in the Torr range at room temperature. The (111) surface of copper (Cu), its most compact and lowest energy surface, became unstable when exposed to carbon monoxide (CO) gas. Scanning tunneling microscopy revealed that at room temperature in the pressure range 0.1 to 100 Torr, the surface decomposed into clusters decorated by CO molecules attached to edge atoms. Between 0.2 and a few Torr CO, the clusters became mobile in the scale of minutes. Density functional theory showed that the energy gain from CO binding to low-coordinated Cu atoms and the weakening of binding of Cu to neighboring atoms help drive this process. Particularly for softer metals, the optimal balance of these two effects occurs near reaction conditions. Cluster formation activated the surface for water dissociation, an important step in the water-gas shift reaction.

Atomic Scale Identification of Coexisting Graphene Structures on Ni(111)

Through a combined scanning tunneling microscopy (STM) and density functional theory (DFT) approach, we provide a full characterization of the different chemisorbed configurations of epitaxial graphene coexisting on the Ni(111) single crystal surface. Top-fcc, top-hcp, and top-bridge are found to be stable structures with comparable adsorption energy. By comparison of experiments and simulations, we solve an existing debate, unambiguously distinguishing these configurations in high-resolution STM images and characterizing the transitions between adjacent domains. Such transitions, described in detail through atomistic models, occur not only via sharp domain boundaries, with extended defects, but predominantly via smooth in-plane distortions of the carbon network, without disruption of the hexagonal rings, which are expected not to significantly affect electron transport.

Local Electronic Structure and Density of Edge and Facet Atoms at Rh Nanoclusters Self-Assembled on a Graphene Template

The chemical and physical properties of nanoclusters largely depend on their sizes and shapes. This is partly due to finite size effects influencing the local electronic structure of the nanocluster atoms which are located on the nanofacets and on their edges. Here we present a thorough study on graphene-supported Rh nanocluster assemblies and their geometry-dependent electronic structure obtained by combining high-energy resolution core level photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory. We demonstrate the possibility to finely control the morphology and the degree of structural order of Rh clusters grown in register with the template surface of graphene/Ir(111). By comparing measured and calculated core electron binding energies, we identify edge, facet, and bulk atoms of the nanoclusters. We describe how small interatomic distance changes occur while varying the nanocluster size, substantially modifying the properties of surface atoms. The properties of under-coordinated Rh atoms are discussed in view of their importance in heterogeneous catalysis and magnetism.

Nanobubbles at GPa Pressure under Graphene.

We provide direct evidence that irradiation of a graphene membrane on Ir with low-energy Ar ions induces formation of solid noble-gas nanobubbles. Their size can be controlled by thermal treatment, reaching tens of nanometers laterally and height of 1.5 nm upon annealing at 1080 °C. Ab initio calculations show that Ar nanobubbles are subject to pressures reaching tens of GPa, their formation being driven by minimization of the energy cost of film distortion and loss of adhesion.

Temperature-Driven Reversible Rippling and Bonding of a Graphene Superlattice

In order to unravel the complex interplay between substrate interactions and film configuration, we investigate and characterize graphene on a support with non-three-fold symmetry, the square Ir(100). Below 500 °C, distinct physisorbed and chemisorbed graphene phases coexist on the surface, respectively characterized by flat and buckled morphology. They organize into alternating domains that extend on mesoscopic lengths, relieving the strain due to the different thermal expansion of film and substrate. The chemisorbed phase exhibits exceptionally large one-dimensional ripples with regular nanometer periodicity and can be reversibly transformed into physisorbed graphene in a temperature-controlled process that involves surprisingly few C-Ir bonds. The formation and rupture of these bonds, rather than ripples or strain, are found to profoundly alter the local electronic structure, changing graphene behavior from semimetal to metallic type. The exploitation of such subtle interfacial changes opens new possibilities for tuning the properties of this unique material.

Dynamics of the O induced reconstruction of the Rh(110) surface: A scanning tunnelling microscopy study

The oxygen adsorption on the unreconstructed Rh(110) surface has been studied by scanning tunnelling microscopy (STM), by imaging the evolution of the surface reconstruction in situ during oxygen uptake at 390 K. The dynamics terminate with the formation of a strained (10×2)–O structure with high local oxygen coverage. Initially, kink atoms are detached from the steps and diffuse over the surface, most probably as Rh–O units, as inferred by comparison to x-ray photoelectron spectroscopy (XPS) data, until they condense in zigzag structures characteristic for the (2×2)p2mg–O structure (0.5 ML). At oxygen doses above 0.12 L, missing rows begin to be dug along the [110] direction into the steps, detaching further Rh atoms. The reconstruction proceeds as a missing/added row reconstruction. With ongoing surface reconstruction, a second reconstruction mechanism of local nature sets in: Rh atoms start to be ejected out of the terraces and condense at the ends of the so formed troughs. Dosing further oxygen on th...

(10×2) strained reconstruction induced by oxygen adsorption on the Rh(110) surface

Oxygen adsorption on the (1×2) missing row reconstructed Rh(110) surface has been studied by means of low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM). Starting from the already known (2×2)p2mg oxygen overlayer in which the substrate is (1×2) reconstructed, further oxygen has been dosed at room and lower temperatures. Upon heating, additional substrate reconstruction takes place and the surface forms a new structure with (10×2) periodicity and high local oxygen coverage. Oxygen 1s XPS measurements show a binding energy shift from 530.25 eV in the (2×2)p2mg to 529.75 eV in the (10×2) layer. Analysis of STM images reveals that in the (10×2) layer, the rhodium close-packed rows are strained and segmented in the [110] direction. On the basis of the experimental results, models for the (10×2) structure and its formation process are proposed and compared with “pseudo-oxide” structures.

Heterogeneous and homogeneous routes in water oxidation catalysis starting from Cu(II) complexes with tetraaza macrocyclic ligands

Since the first report in 2012, molecular copper complexes have been proposed as efficient electrocatalysts for water oxidation reactions, carried out in alkaline/neutral aqueous media. However, in some cases the copper species have been recognized as precursors of an active copper oxide layer, electrodeposited onto the working electrode. Therefore, the question whether copper catalysis is molecular or not is particularly relevant in the field of water oxidation. In this study, we investigate the electrochemical activity of copper(II) complexes with two tetraaza macrocyclic ligands, distinguishing heterogeneous or homogeneous processes depending on the reaction media. In an alkaline aqueous solution, and upon application of an anodic bias to working electrodes, an active copper oxide layer is observed to electrodeposit at the electrode surface. Conversely, water oxidation in neutral aqueous buffers is not associated to formation of the copper oxide layer, and could be exploited to evaluate and optimize a molecular, homogeneous catalysis.

Temperature-Driven Changes of the Graphene Edge Structure on Ni(111): Substrate vs Hydrogen Passivation

Atomic-scale description of the structure of graphene edges on Ni(111), both during and post growth, is obtained by scanning tunneling microscopy (STM) in combination with density functional theory (DFT). During growth, at 470 °C, fast STM images (250 ms/image) evidence graphene flakes anchored to the substrate, with the edges exhibiting zigzag or Klein structure depending on the orientation. If growth is frozen, the flake edges hydrogenate and detach from the substrate, with hydrogen reconstructing the Klein edges.