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High-quality nitrogen-doped graphene on nickel is prepared by exploiting both the catalytic properties of nickel and the solubility of nitrogen atoms into its bulk. Following the standard chemical vapor deposition procedure, a previously nitrogen-doped nickel substrate is exposed to carbon-containing precursors so that nitrogen atoms, segregating to the surface, remain trapped in the growing graphene network. Morphological and chemical characterization by scanning tunneling microscopy and X-ray photoelectron spectroscopy demonstrates that the process yields a flat, wide, continuous nitrogen-doped graphene layer. Experimental results are combined with a thorough density functional theory investigation of possible structural models, to obtain a clear description at the atomic scale of the various configurations of the nitrogen atoms observed in the graphene mesh. This growth method is potentially scalable and suitable for the production of high-performance nano-devices with well-defined nitrogen centers, to be exploited as metal-free carbon-based catalysts in several applicative fields such as electrochemistry, energy storage, gas storage/sensing or wastewater treatment., 21 pages, including 4 figures, plus SI

Under near-ambient pressure conditions, carbon monoxide molecules intercalate underneath an epitaxial graphene monolayer grown on Ni(111), getting trapped into the confined region at the interface. On the basis of ab-initio density functional theory calculations, we provide here a full investigation of the intercalated CO pattern, highlighting the modifications induced on the graphene electronic structure. For a CO coverage as low as 0.14 monolayer (ML), the graphene layer is spatially decoupled from the metallic substrate, with a significant C 1s core level shift towards lower binding energies. The most relevant signature of the CO intercalation is a clear switching of the graphene doping state, which changes from n-type, when strongly interacting with the metal surface, to p-type. The shift of the Dirac cone linearly depends on the CO coverage, reaching about 0.9 eV for the saturation value of 0.57 ML. Theoretical predictions are compared with the results of scanning tunnelling microscopy, low-energy electron diffraction and photoemission spectroscopy experiments, which confirm the proposed scenario for the nearly saturated intercalated CO system. This result opens the way to the application of the graphene/Ni(111) interface as gas sensor to easily detect and quantify the presence of carbon monoxide.

Lateral quantum confinement is of great interest in tuning the electronic properties of graphene-based nanostructures, making them suitable for technological applications. In principle, these properties might be controlled through the edge topology: for example, zigzag nanoribbons are predicted to have spin-polarized edge states. The practical realization of these structures is of utmost importance in fully harnessing the electronic properties of graphene. Here, the formation of regular, 1.4 nm wide ribbon-like graphene structures with zigzag edges are reported, showing 1D electronic states. It is found that these “pseudo-ribbons” embedded in single-layer graphene supported on Ni(100) can spontaneously form upon carbon segregation underneath 1D graphene moiré domains, extending hundreds of nanometers in length. On the basis of both microscopy/spectroscopy/diffraction experiments and theoretical simulations, it is shown that these structures, even though seamlessly incorporated in a matrix of strongly interacting graphene, exhibit electronic properties closely resembling those of zigzag nanoribbons.

Molecules intercalate at the graphene/metal interface even though defect-free graphene is impermeable to any atomic and molecular species in the gas and liquid phase, except hydrogen. The mechanism of molecular intercalation is still a big open question. In this Letter, by means of a combined experimental (STM, XPS, and LEED) and theoretical (DFT) study, we present a proof of how CO molecules succeed in permeating the graphene layer and get into the confined zone between graphene and the Ni(111) surface. The presence of N-dopants in the graphene layer is found to highly facilitate the permeation process, reducing the CO threshold pressure by more than one order of magnitude, through the stabilization of multiatomic vacancy defects that are the open doors to the bidimensional nanospace, with crucial implications for the catalysis under cover and for the graphene-based electrochemistry.

Many applications of molecular layers deposited on metal surfaces, ranging from single-atom catalysis to on-surface magnetochemistry and biosensing, rely on the use of thermal cycles to regenerate the pristine properties of the system. Thus, understanding the microscopic origin behind the thermal stability of organic/metal interfaces is fundamental for engineering reliable organic-based devices. Here, we study nickel porphyrin molecules on a copper surface as an archetypal system containing a metal center whose oxidation state can be controlled through the interaction with the metal substrate. We demonstrate that the strong molecule-surface interaction, followed by charge transfer at the interface, plays a fundamental role in the thermal stability of the layer by rigidly anchoring the porphyrin to the substrate. Upon thermal treatment, the molecules undergo an irreversible transition at 420 K, which is associated with an increase of the charge transfer from the substrate, mostly localized on the phenyl substituents, and a downward tilting of the latters without any chemical modification. This journal is

A novel apparatus devoted to time-resolved photoemission experiments in the sub-picosecond regime will be presented. The system is composed of a Ti:sapphire laser source and a time of flight (TOF) electron energy analyzer mounted in a UHV experimental chamber. The laser source is characterized by a pulse duration of 150 fs at a wavelength of 790 nm (1.57 eV) and operates at a repetition rate of 1 kHz. To perform photoemission measurements, UV radiation up to 6.28 eV is produced with sequential steps of frequency conversion by employing crystals with a second order nonlinearity. Photoelectrons are collected by a TOF spectrometer designed to analyze electrons from tenths of eV up to 5 eV. It can be operated in two different angular resolution modes switching on and off an electrostatic collection optics: the high angular resolution mode (Deltaalpha = +/-2.7degrees) and the low angular resolution mode (Deltaalpha = +/-5.6degrees). Single photon photoemission spectra from the Ag(100) clean surface have been recorded at room temperature using the fourth harmonic light (lambda = 200 nm and hv = 6.28 eV). The Fermi edge profile convoluted with a Gaussian-shaped energy transmission function of the TOF spectrometer sets an upper limit for the energy resolution which is about 65 meV (FWHM) at 2 eV of electron energy.

We study the interplay between competitive substrate-C interaction processes occurring during chemical vapour deposition (CVD) of ethylene on Re(0 00 1). At T < 500 K dissociative ethylene adsorption leads to the formation of a dimer species, producing an ordered (4 x 2) structure. In the range 500-700 K, the formation of a high-quality single-layer of graphene is strongly opposed by the formation of a surface carbide characterised by C trimer units, and, at higher temperatures, by carbon dissolution into the bulk. Our experimental and theoretical results demonstrate that, under UHV conditions, the formation of a long-range ordered graphene layer on Re (0 0 0 1) without carbon bulk saturation is confined to a narrow window of growth parameters: substrate temperature, hydrocarbon gas pressure and exposure time. Our combined experimental and theoretical approach allowed us to validate a concept which had already been anticipated in some earlier works on Rh, Fe and Ni, namely that the epitaxial growth of graphene is not necessarily restricted to surfaces where carburisation is precluded, but could take place, under given appropriate conditions, also on other metallic substrates exhibiting a strong C-substrate interaction. (C) 2014 Elsevier Ltd. All rights reserved.

We have addressed the problem of determining a reliable experimental descriptor of surface chemical reactivity by measuring Pd and Ru 3d(5/2) core-level shifts of the Pd(n)/Ru(0001) pseudomorphic overlayer system (n = 0-3) by high resolution X-ray photoelectron spectroscopy. We find a linear relationship between the calculated theoretical changes of the d-band center position projected on each Ru and Pd atomic layer (which is, according to the Hammer and Norskov d-band model, a good theoretical descriptor of chemical reactivity) and the corresponding core-level shifts, both for the Ru atomic planes and for the Pd overlayers. Core-level shifts, therefore, should be considered as reliable experimental descriptors of chemical reactivity in the same sense (and with similar limitations) of the theoretical descriptor d-band center. Final-state effect contributions to the shifts do not obscure this trend.

Molecular interfaces formed between metals and molecular compounds offer a great potential as building blocks for future opto-electronics and spintronics devices. Here, a combined theoretical and experimental spectro-microscopy approach is used to show that the charge transfer occurring at the interface between nickel tetraphenyl porphyrins and copper changes both spin and oxidation states of the Ni ion from [Ni(II), S = 0] to [Ni(I), S = 1/2]. The chemically active Ni(I), even in a buried multilayer system, can be functionalized with nitrogen dioxide, allowing a selective tuning of the electronic properties of the Ni center that is switched to a [Ni(II), S = 1] state. While Ni acts as a reversible spin switch, it is found that the electronic structure of the macrocycle backbone, where the frontier orbitals are mainly localized, remains unaffected. These findings pave the way for using the present porphyrin-based system as a platform for the realization of multifunctional devices where the magnetism and the optical/transport properties can be controlled simultaneously by independent stimuli., Small;17(50)