Nitrogen doping of graphene is a suitable route to tune the electronic structure of graphene, leading to n-type conductive materials. Herein, we report a simple way to insert nitrogen atoms into graphene by low-energy nitrogen bombardment, forming nitrogen-doped graphene. The formation of nitrogen-doped graphene is investigated with high resolution X-ray photoelectron spectroscopy, allowing to determine the doping level and to identify two different carbon−nitrogen species. By application of different ion implantation energies and times, we demonstrate that a doping level of up to 0.05 monolayers is achievable and that the branching ratio of the two nitrogen species can be varied.
The doping of graphene to tune its electronic structure is essential for its further use in carbon based electronics. Adapting strategies from classical silicon based semiconductor technology, we use the incorporation of heteroatoms in the 2D graphene network as a straightforward way to achieve this goal. Here, we report on the synthesis of boron-doped graphene on Ni (111) calculations. Furthermore, our calculations suggest that doping with boron leads to graphene preferentially adsorbed in the top-fcc geometry, since the boron atoms in the graphene lattice are then adsorbed at substrate fcc-hollow sites. The smaller adsorption distance of boron compared to carbon leads to a bending of the graphene sheet in the vicinity of the boron atoms. By comparing calculations of doped and undoped graphene on Ni(111), as well as the respective free-standing cases, we are able to distinguish between the effects that doping and adsorption have on the band structure of graphene. Both, doping and bonding to the surface, result in opposing shifts on the graphene bands.
We report on experimental and theoretical investigations of nitrogen-doped graphene. The incorporation of nitrogen was achieved during chemical-vapor deposition on Ni(111) using pyridine as a precursor. The obtained graphene layers were investigated using photoelectron spectroscopy. By studying C 1s and N 1s core levels, we show that the nitrogen content is influenced by the growth temperature and determine the atomic arrangement of the nitrogen atoms. Valence-band photoelectron spectra show that the incorporation of nitrogen leads to a broadening of the photoemission lines and a shift of the π band. Density functional calculations for two possible geometric arrangements, the substitution of carbon atoms by nitrogen and vacancies in the graphene sheet with pyridinic nitrogen at the edges, reveal that the two arrangements have opposite effects on the band structure. For the present experimental approach, vacancies with pyridinic nitrogen are dominant. In the latter case the vacancies generated by the nitrogen doping, not the nitrogen itself, have the main effect on the band structure. By intercalating gold between the doped graphene layer and the Ni(111) substrate electronic decoupling is achieved. After intercalation the doping remains
Understanding the adsorption and reaction between hydrogen and graphene is of fundamental importance for developing graphene-based concepts for hydrogen storage and for the chemical functionalization of graphene by hydrogenation. Recently, theoretical studies of single-sided hydrogenated graphene, so called graphone, predicted it to be a promising semiconductor for applications in graphene-based electronics. Here, we report on the synthesis of graphone bound to a Ni(111) surface. We investigate the formation process by X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and density-functional theory calculations, showing that the hydrogenation of graphene with atomic hydrogen indeed leads to graphone, that is, a hydrogen coverage of 1 ML (4.2 wt %). The dehydrogenation of graphone reveals complex desorption processes that are attributed to coverage-dependent changes in the activation energies for the associative desorption of hydrogen as molecular H2 .
The growth and oxidation of graphene supported on Rh(111) was studied in situ by high-resolution X-ray photoelectron spectroscopy. By variation of propene pressure and surface temperature the optimum growth conditions were identified, yielding graphene with low defect density. Oxidation of graphene was studied at temperatures between 600 and 1000 K, at an oxygen pressure of ~2 × 10(-6) mbar. The oxidation follows sigmoidal reaction kinetics. In the beginning, the reaction rate is limited by the number of defects, which represent the active sites for oxygen dissociation. After an induction period, the reaction rate increases and graphene is rapidly removed from the surface by oxidation. For graphene with a high defect density we found that the oxidation is faster. In general, a reduction of the induction period and a faster oxidation occur at higher temperatures.
Graphene grown on Rh(111) was used as a template for the growth of Pd nanoclusters. Using high-resolution synchrotron radiation-based X-ray photoelectron spectroscopy, we studied the deposition of Pd on corrugated graphene in situ. From the XP spectra, we deduce a cluster-by-cluster growth mode. The formation of clusters with 3 nm diameter was confirmed by low-temperature scanning tunneling microscopy measurements. The investigation of the thermal stability of the Pd particles showed three characteristic temperature regimes: Up to 550 K restructuring of the particles takes place, between 550 and 750 K the clusters coalesce into larger agglomerates, and finally between 750 and 900 K Pd intercalates between the graphene layer and the Rh surface.
Nanocluster arrays on graphene (Gr) are intriguing model systems for catalysis. We studied the adsorption and oxidation of CO on Pt/Gr/Rh(111) with synchrotron-based high-resolution X-ray photoelectron spectroscopy. On the nanoclusters, CO is found to adsorb at three different sites: namely, on-top, bridge, and step. The C 1s spectra exhibit remarkable similarities to those on the stepped Pt(355) surface. Similar to the case for stepped Pt surfaces, a clear preference for the adsorption on the step sites is found, while the preference for the adsorption on the on-top site over the bridge site on the terraces is much less pronounced in comparison to that on Pt single crystals. Temperatureprogrammed X-ray photoelectron spectroscopy revealed an enhanced binding energy for the cluster step sites, similar to the situation on stepped Pt surfaces. The oxidation of CO on graphene-supported Pt nanoclusters follows a pseudo-first-order rate law. Applying an Arrhenius analysis, we found an activation energy of 13 ± 4 kJ/mol, which is much smaller than that on Pt(111), due to the more reactive step and kink sites on the nanoclusters.
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