In this paper, we evaluate of the adsorption/ desorption of ammonia molecules on a graphene surface by studying the Fermi level shift. Based on a physically plausible model, the adsorption and desorption rates of ammonia molecules on graphene have been extracted from the measured Fermi level shift as a function of exposure time. An electric field-induced flipping behavior of ammonia molecules on graphene is suggested, based on field effect transistor (FET) measurements.
In this letter we report on transport measurements of epitaxial graphene on SiC(0001) with oxygen adsorption. In a $50\times 50 μ\mathrm{m^2}$ size Hall bar we observe the half-integer quantum Hall effect with a transverse resistance plateau quantized at filling factor around $ν= 2$, an evidence of monolayer graphene. We find low electron concentration of $9\times 10^{11} \textrm{cm}^{-2}$ and we show that a doping of $10^{13}\textrm{cm}^{-2}$ which is characteristic of intrinsic epitaxial graphene can be restored by vacuum annealing. The effect of oxygen adsorption on carrier density is confi…
The oxygen adsorption and dissociation on pristine silicene surface are studied by use of first-principles in this letter. The oxygen adsorption and dissociation on pristine silicene surface are studied by use of first-principles in this letter. It is found that the pristine silicene is not stable in air because the oxygen molecule can be easily adsorbed and dissociated into two O atoms without overcoming any energy barrier on pristine silicene surface. In addition, dissociated oxygen atoms are relatively difficult to migrate on or desorbed from pristine silicene surface, leading to poor mobil…
Adsorption of molecular oxygen on B-, N-, Al-, Si-, P-, Cr- and Mn-doped graphene is theoretically studied using density functional theory in order to clarify if O2 can change the possibility of using doped graphene for gas sensors, electronic and spintronic devices. O2 is physisorbed on B-, and Ndoped graphene with small adsorption energy and long distance from the graphene plane, indicating the oxidation will not happen; chemisorption is observed on Al-, Si-, P-, Cr- and Mn-doped graphene. The local curvature caused by the large bond length of X-C (X represents the dopants) relative to CC bo…
X-ray powder diffraction using a synchrotron light source reveals significant modifications to both morphology and strain state in Palladium nanocubes after oxidation. Short-range strain measured by the static component of the Debye-Waller coefficient is observed to be higher in the oxidized nanoparticles; while long-range strain related to the line broadening of the diffraction peaks is seen to decrease. Using multiscale modelling with classical molecular dynamics and density functional theory, we connect the decrease in long-range strain to the increased truncation of the oxidized nanocubes,…
Both experimental and theoretical studies of the magnetic properties of micrographite and nanographite indicate a crucial role of the partial oxidation of graphitic zigzag edges in ferromagnetism. In contrast to total and partial hydrogenation, the oxidation of half of the carbon atoms on the graphite edges transforms the antiferromagnetic exchange interaction between graphite planes and over graphite ribbons to the ferromagnetic interaction. The stability of the ferromagnetism is discussed.
The effect of oxygen adsorption on the local structure and electronic properties of monolayer graphene grown on SiC(0001) has been studied by means of Low Energy Electron Microscopy (LEEM), microprobe Low Energy Electron Diffraction (\muLEED) and microprobe Angle Resolved Photoemission (\muARPES). We show that the buffer layer of epitaxial graphene on SiC(0001) is partially decoupled after oxidation. The monitoring of the oxidation process demonstrates that the oxygen saturates the Si dangling bonds, breaks some Si-C bonds at the interface and intercalates the graphene layer. Accurate control …
The O2 dissociation and O atoms adsorption on free-standing germanene are studied by using first-principles calculations in this letter. Compared with the spontaneous dissociation of oxygen molecule on free-standing silicene in air, germanene is more stable than silicene from kinetic point of view, with overcoming energy barrier of about 0.55 eV. Especially, in contrast with the unique chemical adsorption of O2-dissociation-induced O atoms on silicene, oxygen molecule can behave a correspondingly stable adsorption on germanene surface. Moreover, single O atom adsorption on germanene is also di…
We study by kinetic Monte Carlo simulations the dynamic behavior of a Ziff-Gulari-Barshad (ZGB) model for the catalytic oxidation of CO on a surface. It is well known that the ZGB model presents a continuous transition between an oxygen poisoned state and a reactive state that it is not observed in nature. Based on some experimental results that indicate that the oxygen atoms move away from each other upon dissociation at the surface, we modify the standard ZGB model by changing the entrance mechanism of the oxygen molecule. We study three different ways in which the oxygen atoms can be adsorb…
Epitaxial silicene, which is one single layer of silicon atoms packed in a honeycomb structure, demonstrates a strong interaction with the substrate that dramatically affects its electronic structure. The role of electronic coupling in the chemical reactivity between the silicene and the substrate is still unclear so far, which is of great importance for functionalization of silicene layers. Here, we report the reconstructions and hybridized electronic structures of epitaxial 4x4 silicene on Ag(111), which are revealed by scanning tunneling microscopy and angle-resolved photoemission spectrosc…
Using first-principles calculations within density functional theory we demonstrate that the adsorption of single oxygen atom results in significant electron transfer from graphene to oxygen. This strongly disturbs the charge landscape of the C-C bonds at the proximity. Additional oxygen atoms adsorbing to graphene prefer always the C-C bonds having highest charge density and consequently they have tendency to form domain structure. While oxygen adsorption to one side of graphene ends with significant buckling, the adsorption to both sides with similar domain pattern is favored. The binding en…
van der Waals (vdW) interaction plays a fundamental role in the surface-molecules related phenomena. Tuning of the correlated charge fluctuation in the vdW complex is a plausible way to modulate the molecules interaction at the atomic surface. We report vdW interaction tunability of the graphene-CO$_2$ complex by combining the first principle calculations with the vdW exchange correlation density functionals and the time evaluation measurements of CO$_2$ molecules adsorption/desorption on graphene under an external electric field. The field-dependent charge transfer within the complex unveils …
We investigate the adsorption of cobalt phthalocyanine (CoPc) molecules on a thin layer of cobalt oxide grown on Ir(100). To that end we compare the results of low-temperature scanning tunneling microscopy (STM) with those of ab-initio density functional theory (DFT) calculations and reveal the adsorption geometry. We find that the CoPc molecules lie flat on the surface and that their central cobalt atom forms a chemical bond to a substrate oxygen ion. However, this bond contributes only modestly to the adsorption energy, while van-der-Waals forces dominate the potential landscape and determin…
The chemical reactivity of graphene under ultraviolet (UV) light irradiation is investigated under positive and negative gate electric fields. Graphene edges are selectively etched when negative gate voltages are applied, while the reactivity is significantly suppressed for positive gate voltages. Oxygen adsorption onto graphene is significantly affected by the Fermi level of the final state achieved during previous electrical measurements. UV irradiation after negative-to-positive gate sweeps causes predominant oxygen desorption, while UV irradiation after gate sweeps in the opposite directio…
The adsorption of the chiral molecule lactic acid on chiral Pt surfaces is studied by Density Functional Theory calculations. First we study the adsorption of L-lactic acid on the flat Pt(111) surface. Using the oPBE-vdW functional which includes van der Waals forces on an ab initio level, it is shown that the molecule has two binding sites, a carboxyl and the hydroxyl oxygen atoms. Since real chiral surfaces are (i) known to undergo thermal roughening that alters the distribution of kinks and step edges but not the overall chirality and (ii) kink sites and edge sites are usually the energetic…
Exotic and robust metallic surface states of topological insulators (TIs) have been expected to provide a promising platform for novel surface chemistry and catalysis. However, it is still an unprecedented field how TIs affect the activity of catalysts. In this work, we study the effects of topological surface states (TSSs) on the activity of transition metal clusters (Au, Ag, Cu, Pt, and Pd), which are supported on a TI Bi2Se3 substrate. It was found the adsorption energy of oxygen on the supported catalysts can be always enhanced due to the TSSs. However, it does not necessarily mean an incr…
We study the interaction of H$_2$, O$_2$, CO, H$_2$O and OH molecules with the vacancy defects of graphene and silicene. Atoms around the bare vacancy reconstruct and specific chemically active sites are created. While H$_2$, O$_2$ and CO remain intact on both pristine graphene and silicene, these molecules can dissociate when they are placed at the close proximity of these chemically active sites and nucleate centers for the hydrogenation and oxygenation. Saturation of the dangling bonds at the defect sites by constituent atoms of dissociated molecules gives rise to significant modification o…
We study the binding pattern of the amino acid alanine on the naturally chiral Pt surfaces Pt(531), Pt(321) and Pt(643). These surfaces are all vicinal to the {111} direction but have different local environments of their kink sites and are thus a model for realistic roughened Pt surfaces. Alanine has only a single methyl group attached to its chiral center, which makes the number of possible binding conformations computationally tractable. Additionally, only the amine and carboxyl group are expected to interact strongly with the Pt substrate. On Pt(531) we study the molecule in its pristine a…
Electron paramagnetic resonance (EPR) study of air-physisorbed defective carbon nano-onions evidences in favor of microwave assisted formation of weakly-bound paramagnetic complexes comprising negatively-charged O2- ions and edge carbon atoms carrying pi-electronic spins. These complexes being located on the graphene edges are stable at low temperatures but irreversibly dissociate at temperatures above 50-60 K. These EPR findings are justified by density functional theory (DFT) calculations demonstrating transfer of an electron from the zigzag edge of graphene-like material to oxygen molecule …
