The mechanism of metal corrosion passivation

The main regularities of variations in the thermodynamic properties of components of cubic vanadium carbide, depending on the composition in the region of homogeneity, are investigated experimentally. It is believed that these regularities are inherent only to metal oxides. This serves as the basis for the concept that passivation during the corrosion of metals occurs due to the formation of surface metal oxide whose composition corresponds to the maximum concentration of oxygen in the region of homogeneity. The thermodynamic stimulus of corrosion is in this case reduced to almost zero.     

Thermal stability of graphene edge structure and graphene nanoflakes

One of the most exciting recent developments in nanoscience was the discovery of graphene (single sheets of carbon atoms, a two-dimensional "(2D) crystal") and the subsequent discovery of the fascinating properties of this new material, e.g., electrons behaving as massless relativistic particles and an anomalous quantum Hall effect [A. K. Geim and K. S. Novoselov, Nat. Mater. 6, 183 (2007)]. It is also surprising that large sheets of graphene exist as it was widely believed that 2D crystals are unstable. Furthermore, because of the stability of folded graphene sheets, i.e., carbon nanotubes (CNTs), a fascinating question is why does not graphene spontaneously transform into CNTs? In this paper, we explore the thermal stability of small pieces of graphene, i.e., graphene nanoflakes by ab initio quantum mechanical techniques. We find that indeed nanoflakes are stable to being heated and do not under any conditions used here transform to CNTs. They do not, however, remain strictly 2D as at finite temperatures, they undergo extensive vibrational motion and remain buckled if annealed and then quenched to room temperature.     

Graphene nucleation on transition metal surface: structure transformation and role of the metal step edge

The nucleation of graphene on a transition metal surface, either on a terrace or near a step edge, is systematically explored using density functional theory calculations and applying the two-dimensional (2D) crystal nucleation theory. Careful optimization of the supported carbon clusters, C(N) (with size N ranging from 1 to 24), on the Ni(111) surface indicates a ground state structure transformation from a one-dimensional C chain to a 2D sp(2) C network at N ≈ 10-12. Furthermore, the crucial parameters controlling graphene growth on the metal surface, nucleation barrier, nucleus size, and nucleation rate on a terrace or near a step edge are calculated. In agreement with numerous experimental observations, our analysis shows that graphene nucleation near a metal step edge is superior to that on a terrace. On the basis of our analysis, we propose the use of graphene seeds to synthesize high-quality graphene in large area.     

Chemical surface passivation of Ge nanowires

Surface oxidation and chemical passivation of single-crystal Ge nanowires with diameters ranging between 7 and 25 nm were studied. The surface chemistry differs significantly from that of well-studied monolithic atomically smooth single-crystal substrates. High-resolution Ge 3d XPS measurements reveal that Ge nanowires with chemically untreated surfaces exhibit greater susceptibility to oxidation than monolithic Ge substrates. Multiple solution-phase routes to Ge nanowire surface passivation were studied, including sulfidation, hydride and chloride termination, and organic monolayer passivation. Etching in HCl results in chloride-terminated surfaces, whereas HF etching leads to hydride termination with limited stability. Exposure to aqueous ammonium sulfide solutions leads to a thick glassy germanium sulfide layer. Thermally initiated hydrogermylation reactions with alkenes produce chemically stable, covalently bonded organic monolayer coatings that enable ohmic electrical contacts to be made to the nanowires.     

Transition metal ions-doped polyaniline/graphene oxide nanostructure as high performance electrode for supercapacitor applications

Journal of Solid State Electrochemistry - Polyaniline/graphene oxide (PANI/GO) co-doped with Zn2+ and Fe3+ was synthesized via a simple and low cost one-step chronoamperometry method on stainless...     

Xanes studies of III-V semiconductor surface passivation

III-V semiconductor surfaces are known to be very reactive in air due to the presence of unsaturated dangling bonds (DBs). Native oxides are highly undesirable in many device applications. Remarkable progress has been made in recent years in the preparation of air-stable surfaces by wet chemical etching. XANES studies have shown that the stability of the passive surface is due to termination of surface DBs through the formation of an ordered overlayer selfassembled in chemical solutions. For a (100) InP surface, saturation of two adjacent DBs is achieved by the formation of In-S-In bridge bonds along the [011] direction. A refined analysis of σ-resonance indicates that XANES data are consistent with a recently proposed (2×2) InP(100)-S structure where the S is located on bridge sites to form twisted short and long dimers. For the GaAs(111) surface, the surface DBs are terminated by monovalent Ga-Cl bonds along the surface normal.     

Transition metal compound surfaces

Studies of transition metal compound surfaces using modern surface science techniques are reviewed. Studies of the surface structure and composition of model transition metal compound surfaces are emphasized. The growth of the transition metal compound surface from a chemisorbed layer is used as an introduction to investigations of the surface properties of macroscopic single crystals of transition metal compounds. Examples of both binary and tenary compound systems are examined in relation to chemisorbed layer studies. Although only a few systems are chosen to illustrate work in this field, extensive references to other studies and other systems are included.     

Transition metal coated fullerenes

Compound clusters of fullerene molecules and transition metal atoms having the composition C₆₀M_x and C₇₀M_x with x = 0..150 and M ∈ {Ti, Zr, V, Y, Ta, Nb} were produced using laser vaporisation in a low-pressure inert gas aggregation cell. Intensity anomalies in the mass spectra correlate with the atomic radii of the different metals indicating the formation of complete metal layers around the central fullerene molecule. Using high laser intensities the metal-fullerene clusters can be transformed into metcars and metal-carbides. Photofragmentation spectra of preselected C₆₀Ta_x indicate that the fullerene cage is destroyed for x ≥ 3.     

Unique chemical reactivity of a graphene nanoribbon's zigzag edge

The zigzag edge of a graphene nanoribbon possesses a unique electronic state that is near the Fermi level and localized at the edge carbon atoms. The authors investigate the chemical reactivity of these zigzag edge sites by examining their reaction energetics with common radicals from first principles. A "partial radical" concept for the edge carbon atoms is introduced to characterize their chemical reactivity, and the validity of this concept is verified by comparing the dissociation energies of edge-radical bonds with similar bonds in molecules. In addition, the uniqueness of the zigzag-edged graphene nanoribbon is further demonstrated by comparing it with other forms of sp2 carbons, including a graphene sheet, nanotubes, and an armchair-edged graphene nanoribbon.     

Half-metallicity in graphene nanoribbons with topological defects at edge

We report first principles studies of zigzag edged graphene nanoribbons (ZGNR) with one edge partially covered by topological defects. With increasing coverage of an edge by pentagons and heptagons, which are two of the simplest topological defects possible in a graphenic lattice, ZGNRs evolve from a magnetic semiconductor to a ferromagnetic metal. This evolution can be intermediated by a narrow bandgap half-metallic phase, upon suitable concentration and conformation of defects at the edge. Spin-frustration induced by topological defects lead to substantial lowering of magnetic ordering and localization of defect-states in the vicinity of the defects. Dispersion of bands constituted by the defect-states within the bandgap of the corresponding unmodified ZGNR, leads to availability of energy windows for spin-polarized electron transport. Driven primarily by exchange interactions, the energy window for transport of electrons near Fermi energy, is consistently wider and more prevalent for the minority spin, in the entire class of ZGNRs with discontinuous patches of topological defects at an edge. Such defects have been widely predicted and observed to be naturally present at the interfaces in polycrystalline graphene, and can even be formed through chemical and physical processes. Our approach thus may lead to a feasible strategy to manifest workable half-metallicity in ZGNRs without involving non-carbon dopants or functional groups.     

Transition metal complexes of thioalcanamines

Summary Thioalcanamines, in which the N and S atoms are separated by two carbons, induce remarkable schistosomicidal behaviour in laboratory mice infected with the disease, a biological action which might arise from complexation of these potential ligands with metal ions. A study showed that it is possible to obtain both mono- and trimetallic complexes, and the latter can be either homo- or heterometallic.