Structural and electronic properties of graphene nanotube-nanoribbon hybrids

The structural and electronic properties of a hybrid of an armchair graphene nanotube and a zigzag graphene nanoribbon are investigated by first-principles spin-polarized calculations. These properties strongly depend either on the nanotube location or on the spin orientation. The interlayer spacing, the transverse distance from the center of the ribbon and the stacking configuration affect the electronic structures. The antiferromagnetic configuration has a lower total energy than the ferromagnetic one. The interlayer atomic interactions between the two subsystems would change the low energy dispersions, open subband spacings, and induce more band-edge states. Moreover, such interactions create an energy gap and break the spin degeneracy in the antiferromagnetic configuration. The band-edge-state energies are sensitive to the nanotube location.     

Effects of heteroatoms on the electronic,sensor, and adsorption properties of graphene

The effects of doping heteroatoms on the structure, electronic and adsorption properties of graphene are investigated using density functional theory calculations. Six different doped graphenes (with Al, B, Si, N, P, and S) are considered, and to obtain the interaction and adsorption properties, three sulfur-containing molecules (H₂S, SO₂, and thiophene) were interacted with selected graphenes. The adsorption energies (E _ad) in the gas phase and solvents show the exothermic interaction for all complexes. The maximum E _ad values are observed for aluminum doped graphene (AG) and silicon doped graphene (SiG), and adsorption energies in the solvent are not so different from those in the gas phase. NBO calculations show that the AG and SiG complexes have the highest E ⁽²⁾ interaction energies and simple graphene (G) and nitrogen doped graphene (NG) have the least E ⁽²⁾ energies. Population analyses show that doping heteroatoms change the energy gap. This gap changes more during the interaction and these changes make these structures useful in sensor devices. All calculated data confirm better adsorption of SO₂ by graphenes versus H₂S and thiophene. Among all graphenes, AG and then SiG are the best adsorbents for these structures.     

Influence of borohydride concentration on the synthesized Au/graphene nanocomposites for direct borohydride fuel cell

Au/graphene nanocomposites are prepared via a one-pot chemical reduction process at room temperature, using graphene oxide (GO) and chloroauric acid (HAuCl₄) as precursors. The obtained Au/graphene nanocomposites are characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). TEM shows that the Au nanoparticles with size of approximately 8.7 nm disperse randomly on the surface of graphene. XPS confirms that the Au/graphene nanocomposites show a higher atomic percentage of C/O (6.3/1), in contrast to its precursor GO (2.2/1). Electrochemical studies reveal that the Au/graphene nanocomposites have electrochemically active surface area of 9.82 m² g^?1. Besides, the influence of borohydride concentration on the as-prepared Au/graphene nanocomposites is investigated in details by cyclic voltammetry, chronoamperometry, and chronopotentiometry. The results indicate that high concentration of borohydride can significantly improve the electrochemical performance of the Au/graphene catalyst.     

Structural and Conductive Characteristics of Fe/Co Nanotubes

The properties of Fe/Co nanotubes, which were fabricated by the method of electrochemical template synthesis, are studied. It is shown that the atomic ratio between the metals in the nanotubes shifts in the direction of cobalt with increasing potential difference during their synthesis; the geometric parameters of nanotubes, in particular, the wall thickness, also vary. Using the X-ray diffraction analysis, it was found that an increase in the concentration of cobalt in the crystal structure of nanotubes leads to a decrease in the interplanar distance and an increase in the conductivity.     

DFT computational study towards investigating Cladribine anticancer drug adsorption on the graphene and functionalized graphene

Structural Chemistry - Density functional theory calculations at the M06-2X/6-31G** level have been carried out to examine the adsorption behavior of Cladribine drug on the graphene and graphene...     

Effects of molecular adsorption on the electronic structure of single-layer graphene

The interaction of small molecules (CCl(4), CS(2), H(2)O, and acetone) with single-layer graphene (SLG) has been studied under steady-state conditions using infrared multiple-internal-reflection spectroscopy. Adsorption results in a broad and intense absorption band, spanning the ～200 to 500 meV range, which is attributed to electronic excitation. This effect, which has not previously been reported for SLG, has been further investigated using dispersion-corrected density functional theory to model the adsorption of H(2)O on SLG supported on an SiO(2) substrate. However, the ideal and defect-free model does not reproduce the observed adsorption-induced electronic transition. This and other observations suggest that the effect is extrinsic, possibly the result of an adsorption-induced change in the in-plane strain, with important differences arising between species that form liquid-like layers under steady-state conditions and those that do not. Furthermore, the C-H stretching modes of CH(2) groups, incorporated in the SLG as defects, undergo nonadiabatic coupling to the electronic transition. This leads to pronounced antiresonance effects in the line shapes, which are analyzed quantitatively. These results are useful in understanding environmental effects on graphene electronic structure and in demonstrating the use of the vibrational spectroscopy of H-containing defects in characterizing SLG structure.     

Transport properties of Nafion membranes modified with tetrapropylammonium ions for direct methanol fuel cell application

This work presents a study of transport properties (proton conductivity, methanol permeability, and water uptake) and acid-base properties of commercial Nafion-112, -115, and -117 membranes modified with tetrapropylammonium (TPA) cations. In the interaction between TPA hydroxide and protons of sulfonate groups in the Nafion matrix, some of the protons are shown to be bound to sulfonate groups and do not participate in transport processes. These findings are confirmed by IR spectroscopy, acid-base titration, and data on proton conductivity of the modified membranes. Proton conductivity of the modified membranes is shown to be effectively described by a percolation model with parameters that agree with published data for commercial Nafion membranes. Based on these results, a model is proposed for the interaction of TPA cations with the sulfonate groups in Nafion membranes. According to this model, TPA cations form hydrophobic clusters in hydrophilic regions of the polymer matrix, thus preventing some of the protonated sulfonate groups from participating in transport processes.     

Microstructural and metal-support interactions of the Pt-CeO2/C catalysts for direct methanol fuel cell application

To understand the ceria promotion effect of Pt-CeO(2)/C catalysts on methanol oxidation, microstructural and metal-oxide interactions of Pt-CeO(2)/C catalysts with an atomic ratio of Pt/Ce between 0.14 and 1.4 were systematically examined using high-resolution transmission electron microscopy and electron energy loss spectroscopy (EELS). With an increasing Pt content in the catalysts, Pt particles gradually invaded into the ceria supports and decoration on Pt particles was observed. Simultaneously, the morphology of the supports was dramatically modified with nanocrystalline and amorphous ceria formed between and/or around the Pt particles. It reveals that the Pt-ceria interaction could take place in the catalysts and the influence of the interaction was enhanced with an increasing Pt/Ce ratio. The EELS study demonstrated that the strong Pt-ceria interaction was related to the redox reaction between Pt and ceria. Experimental results also suggested that the strong interaction between Pt and ceria could contribute to the promotion effect of ceria on the oxidation of methanol.     

Electronic structure and magnetic properties of the graphene/Fe/Ni111 intercalation-like system

The electronic structure and magnetic properties of the graphene/Fe/Ni(111) system were investigated via combination of the density functional theory calculations and electron-spectroscopy methods. This system was prepared via intercalation of thin Fe layers (1 ML) underneath graphene on Ni(111) and its inert properties were verified by means of photoelectron spectroscopy. Intercalation of iron in the space between graphene and Ni(111) changes drastically the magnetic response from the graphene layer that is explained by the formation of the highly spin-polarized 3d(z(2)) quantum-well state in the thin iron layer.     

Structural and electronic effects on the reactivity of carbamoylsilanes towards acrylonitrile addition

The effect of substituents on Si and N on t_1/2 values in the addition of carbamoylsilanes to acrylonitrile was explored. After examination of steric and structural parameters, the best correlation was found to be that rates increased with a decrease in the ionization potential of the carbamoylsilane.     

Hierarchical interactions and their influence upon the adsorption of organic molecules on a graphene film

The competition between intermolecular interactions and lateral variations in the molecule-substrate interactions has been studied by scanning tunneling microscopy (STM), comparing the phase formation of (sub)monolayers of the organic molecule 2,4'-BTP on buckled graphene/Ru(0001) and Ag(111) oriented thin films on Ru(0001). On the Ag films, the molecules form a densely packed 2D structure, while on graphene/Ru(0001), only the areas between the maxima are populated. The findings are rationalized by a high corrugation in the adsorption potential for 2,4'-BTP molecules on graphene/Ru(0001). These findings are supported by temperature programmed desorption (TPD) experiments and theoretical results.     

Preparation and characterization of CPPO/BPPO blend membranes for potential application in alkaline direct methanol fuel cell

A series of hydroxyl-conducting anion-exchange membranes were prepared by blending chloroacetylated poly(2,6-dimethyl-1,4-phenylene oxide) (CPPO) with bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO), and their fuel cell-related performances were evaluated. The resulting membranes exhibited high hydroxyl conductivities (0.022–0.032 S cm⁻¹ at 25 °C) and low methanol permeability (1.35 × 10⁻⁷ to 1.46 × 10⁻⁷ cm² s⁻¹). All the blend membranes proved to be miscible or partially miscible under the investigations of scanning electron microscopy (SEM) and differential scanning calorimeters (DSC). By condition optimization, the blend membranes with 30–40 wt% CPPO are recommended for application in direct methanol alkaline fuel cells because they showed low methanol permeability, excellent mechanical properties and comparatively high hydroxyl conductivity.     

Molecular and electronic structures and magnetic properties of multilayer graphene nanoclusters and their changes under the influence of adsorbed molecules

The results of investigations of the structures and properties of multilayer graphene nano-clusters (nanographites), structural blocks of activated carbon fibers, and their changes under the influence of adsorbed molecules are presented. The presence of specific edge p-electron-ic states in the nanographites and a reversible decrease in their density at the Fermi level upon the interaction of the graphite nanoparticles with adsorbed molecules of oxygen, chlorine, and water were found. The explanation of the discovered effect was proposed in the terms of the model of spin splitting of edge p-electronic states initiated by the transfer of a small fraction of the electron density from the nanographites to adsorbed molecules. The change in the sign of the temperature coefficient of current carrier spin relaxation rate in the presence of adsorbates can be accounted for by their interaction with edge spin-split (magnetically ordered) states. The preservation of peripheral p-electronic states of the nanographites of free (dangling) s-orbitals of edge carbon atoms at saturation with chlorine was substantiated.     

Effect of the fuel electrode composition and structure on the performance of the direct methanol fuel cell

The effect the composition and structure of the active layer of the anode exerts on the performance of the solid-polymer direct methanol fuel cell is studied experimentally. It is shown that the ohmic voltage losses in the layer and the content of the solid polymer electrolyte (SPE) play an important role. The performance of the fuel cells is the best at 20–25 vol % SPE in the layer.     

Changes in the electronic structure and properties of graphene induced by molecular charge-transfer

Interaction with electron-donor and -acceptor molecules such as aniline and nitrobenzene brings about marked changes in the D, G, G' and 2D bands of the Raman spectrum and the electronic structure of graphene, prepared by the exfoliation of graphitic oxide.     

Selective adsorption behaviors of guest molecules COR in the hexamer host networks at liquid/solid interface

Here,the selective adsorption behaviors of guest molecule COR in two hexamer host grids were investigated by means of scanning tunnelling microscope(STM).The assembled structures of small functional organic molecules TTBTA and TATBA were thermodynamically stable.Interestingly,the introduction of the guest molecule COR destroyed the original hexamer structure of TTBTA and combined with it to form a new triangular host-guest system.Different from TTBTA,the introduction of the guest molecule COR did not affect the six-membered ring structure of TATBA.Furthermore,the co-assembly structure of TTBTA/TATBA/COR was established and the guest molecule COR showed preferential adsorption to the TATBA host grid.Density functional theory(DFT) calculations had been performed to disclose the mechanism of the involved assemblies.     

Synthesis of PtRu nanoparticles from the hydrosilylation reaction and application as catalyst for direct methanol fuel cell

Nanosized Pt, PtRu, and Ru particles were prepared by a novel process, the hydrosilylation reaction. The hydrosilylation reaction is an effective method of preparation not only for Pt particles but also for other metal colloids, such as Ru. Vulcan XC-72 was selected as catalyst support for Pt, PtRu, and Ru colloids, and TEM investigations showed nanoscale particles and narrow size distribution for both supported and unsupported metals. All Pt and Pt-rich catalysts showed the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure, whereas the Ru and Ru-rich alloys were more typical of a hexagonal close-packed (hcp) structure. As evidenced by XPS, most Pt and Ru atoms in the nanoparticles were zerovalent, except a trace of oxidation-state metals. The electrooxidation of liquid methanol on these catalysts was investigated at room temperature by cyclic voltammetry and chronoamperometry. The results concluded that some alloy catalysts showed higher catalytic activities and better CO tolerance than the Pt-only catalyst; Pt56Ru44/C have displayed the best electrocatalytic performance among all carbon-supported catalysts.     

Preparation of graphene/zeolite composites and the adsorption of pollutants in water

Russian Journal of Applied Chemistry - Based on the advantages of graphene and zeolite, respectively, the graphene/zeolite composites with core-shell structure were synthesized. The features of the...