Role of SnO2 Nanoparticles for a Self-Forming Barrier Layer on a Mild Steel Surface in Hydrochloric Acid Medium Containing Piper betle Leaf Extract.

The self-formation of a porous organic thin-film via corrosion inhibitor supports wide applications of carbon steel in industry. Unfortunately, serious damages could be concentrated to the pinhole and/or pore locations in the porous organic film, resulting in the localized corrosion even when an optimal concentration of organic corrosion inhibitors is used. In this work, SnO2 nanoparticles are used for producing the more robust barrier layer via the self-migration of nanoparticles, resulting in a higher corrosion resistance, smooth and uniform protective layer, as well as the existence of SnO2 in the protective layer that could directly affect the high inhibition performance. Therefore, the work suggests a new way to make a more robust thin film that could extend the use of organic corrosion inhibitors.

Intraconfigurational Transition due to Surface-Induced Symmetry Breaking in Noncovalently Bonded Molecules.

The interaction of molecules with surfaces plays a crucial role in the electronic and chemical properties of supported molecules and needs a comprehensive description of interfacial effects. Here, we unveil the effect of the substrate on the electronic configuration of iron porphyrin molecules on Au(111) and graphene, and we provide a physical picture of the molecule-surface interaction. We show that the frontier orbitals derive from different electronic states depending on the substrate. The origin of this difference comes from molecule-substrate orbital selective coupling caused by reduced symmetry and interaction with the substrate. The weak interaction on graphene keeps a ground state configuration close to the gas phase, while the stronger interaction on gold stabilizes another electronic solution. Our findings reveal the origin of the energy redistribution of molecular states for noncovalently bonded molecules on surfaces.

Direct Observation of the Reduction of a Molecule on Nitrogen Pairs in Doped Graphene.

Incorporating functional atomic sites in graphene is essential for realizing advanced two-dimensional materials. Doping graphene with nitrogen offers the opportunity to tune its chemical activity with significant charge redistribution occurring between molecules and substrate. The necessary atomic scale understanding of how this depends on the spatial distribution of dopants, as well as their positions relative to the molecule, can be provided by scanning tunneling microscopy. Here we show that a noncovalently bonded molecule such as CoPc undergoes a variable charge transfer when placed on N-doped graphene; on a nitrogen pair, it undergoes a redox reaction with an integral charge transfer whereas a lower fractional charge transfer occurs over a single nitrogen. Thus, the charge state of molecules can be tuned by suitably tailoring the conformation of dopant atoms.

Substrate temperature dependence of the crystalline quality for the synthesis of pure-phase MoTe2 on graphene/6H-SiC(0001) by molecular beam epitaxy.

MoTe2 has two stable solid phases. 2H-MoTe2 is semiconducting while 1T' is semimetallic. The selective synthesis of pure-phase thin films is still challenging. In this study, we have investigated the growth temperature dependence of MoTe2 synthesized by molecular beam epitaxy and have identified the optimum temperature for growing the stoichiometric films. It is confirmed that the crystalline quality of MoTe2 strongly depends on the substrate temperature. Post-growth annealing of grown layers at 400 °C stabilizes the semiconducting phase. The structural properties and the phase change in our materials are analyzed in details by reflection high energy electron diffraction, low energy electron diffraction, auger electron spectroscopy, x-ray photoemission spectroscopy, and scanning tunneling microscopy.

Controlling Hydrogen-Transfer Rate in Molecules on Graphene by Tunable Molecular Orbital Levels.

Molecular switches are building blocks of potential interest to store binary information, especially when they can be organized in periodic lattices. Among the variety of possible systems, switches based on hydrogen transfer are of special importance because they allow the switching operation to occur without severe conformational change that may interfere with neighboring molecular units. We have studied the excitation process of hydrogen transfer inside porphyrin molecules assembled on a graphene surface, using a low-temperature scanning tunneling microscope. We show that this hydrogen transfer is induced by an electronic resonant tunneling process through the molecular orbitals. Using nitrogen doping of graphene, we tune the rate of hydrogen transfer by shifting the molecular orbital energies owing to the charge transfer at nitrogen dopant sites in the graphene lattice. The control of the switching process allows the storage of information inside a molecular lattice, which is demonstrated by writing an artificial pattern inside a molecular island.

Molecular adsorbates as probes of the local properties of doped graphene.

Graphene-based sensors are among the most promising of graphene's applications. The ability to signal the presence of molecular species adsorbed on this atomically thin substrate has been explored from electric measurements to light scattering. Here we show that the adsorbed molecules can be used to sense graphene properties. The interaction of porphyrin molecules with nitrogen-doped graphene has been investigated using scanning tunneling microscopy and ab initio calculations. Molecular manipulation was used to reveal the surface below the adsorbed molecules allowing to achieve an atomic-scale measure of the interaction of molecules with doped graphene. The adsorbate's frontier electronic states are downshifted in energy as the molecule approaches the doping site, with largest effect when the molecule sits over the nitrogen dopant. Theoretical calculations showed that, due to graphene's high polarizability, the adsorption of porphyrin induces a charge rearrangement on the substrate similar to the image charges on a metal. This charge polarization is enhanced around nitrogen site, leading to an increased interaction of molecules with their image charges on graphene. Consequently, the molecular states are stabilized and shift to lower energies. These findings reveal the local variation of polarizability induced by nitrogen dopant opening new routes towards the electronic tuning of graphene.

Charge transfer and electronic doping in nitrogen-doped graphene.

Understanding the modification of the graphene's electronic structure upon doping is crucial for enlarging its potential applications. We present a study of nitrogen-doped graphene samples on SiC(000) combining angle-resolved photoelectron spectroscopy, scanning tunneling microscopy and spectroscopy and X-ray photoelectron spectroscopy (XPS). The comparison between tunneling and angle-resolved photoelectron spectra reveals the spatial inhomogeneity of the Dirac energy shift and that a phonon correction has to be applied to the tunneling measurements. XPS data demonstrate the dependence of the N 1s binding energy of graphitic nitrogen on the nitrogen concentration. The measure of the Dirac energy for different nitrogen concentrations reveals that the ratio usually computed between the excess charge brought by the dopants and the dopants' concentration depends on the latter. This is supported by a tight-binding model considering different values for the potentials on the nitrogen site and on its first neighbors.

Grain boundaries in graphene on SiC(0001Ì ) substrate.

Grain boundaries in epitaxial graphene on the SiC(0001̅) substrate are studied using scanning tunneling microscopy and spectroscopy. All investigated small-angle grain boundaries show pronounced out-of-plane buckling induced by the strain fields of constituent dislocations. The ensemble of observations determines the critical misorientation angle of buckling transition θc = 19 ± 2°. Periodic structures are found among the flat large-angle grain boundaries. In particular, the observed θ = 33 ± 2° highly ordered grain boundary is assigned to the previously proposed lowest formation energy structural motif composed of a continuous chain of edge-sharing alternating pentagons and heptagons. This periodic grain boundary defect is predicted to exhibit strong valley filtering of charge carriers thus promising the practical realization of all-electric valleytronic devices.

Random laser action of ZnO@mesoporous silicas.

ZnO@mesoporous silica nanocomposite was prepared by the impregnation method, and very efficient laser action was highlighted. As revealed by high-resolution transmission electron microscopy (HR-TEM), nanometric ZnO particles are confined inside the mesochannels of CMI-1 mesoporous silicas. Upon excitation at 3.6 eV of a femtosecond pulsed laser and at low pumping intensity, the ZnO@mesoporous silica showed a broad photoluminescence (PL) band corresponding to the excitonic recombination of ZnO. When the pumping intensity is increased up to a threshold (2.5 mJ cm(-2)), the excitonic emission turns to stimulated emission through a mechanism which will be discussed. The same threshold value was obtained with another excitation source and nanocomposites with different ZnO loadings inside the CMI-1 mesoporous silica. These results allow a better understanding of the random laser effect in ZnO@mesoporous silica and, consequently, a model has been proposed to explain this phenomenon. Based on these new observations, many new applications can be considered since short-wavelength devices are required by industry to design new information storage supports.