Synthesis of SnO2 nanoribbons by a carbothermal reduction process

This communication describes, for the first time, the growth of SnO2 nanoribbons by a controlled carbothermal reduction process. An analysis of the transmission electron microscopy image revealed that these nanoribbons have a well-defined shape, with a typical width in the range of 70-300 nm. In general, the nanostructured ribbons were more than 100 mum in length. The results reported here support the hypothesis that this ribbon-like nanostructured material grows by a vapor-solid process. This study introduces two hypotheses to explain the SnO2 nanoribbon growth process.

Dióxido de estanho nanoestruturado: síntese e crescimento de nanocristais e nanofitas

The objectives of this work are to supply a basic background on nanostructured materials and also to report about the obtaining of nanoparticles, mainly, tin dioxide nanocrystalline particles (obtained by using the polymeric precursor method) presenting a high stability against particle growth due to the usage of a metastable solid solution. The synthesis and growth of SnO2 nanoribbons by a carbothermal reduction process are also discussed.

Piezomagnetic behavior of Co-doped ZnO nanoribbons

Using ab initio total energy calculations, we show that bilayer systems of ZnO nanoribbons, (ZnO)(2)NR, doped with Co atoms exhibit a piezomagnetic behavior. We find the formation of energetically stable zigzag chains of Co atoms along the edge sites of (ZnO)(2)NR's, Co(Zn(chain))-(ZnO)(2)NR. At the ground state, the antiferromagnetic and the ferromagnetic states are very close in energy, whereas upon longitudinal stretch, parallel to the nanoribbon growth direction, it becomes ferromagnetic. Further electronic structure calculations indicate that not only the magnetic state but also the electronic structure of CoZn(chain)-(ZnO)(2)NR can be tuned by the mechanical stretch. In this case, we find that stretched NR's exhibit dispersive unpaired electronic states within the (ZnO)(2)NR band gap.

Mn dimers on graphene nanoribbons: An ab initio study

We show, using ab initio density functional theory calculations, that Mn dimers adsorbed on graphene nanoribbons (Mn(2)/GNRs) present a magnetic bistability, as does the isolated Mn dimer. Our total energy results indicate that Mn dimers lying along the edge sites of zigzag GNRs represent the most likely configuration. We find that similar to the isolated Mn(2) molecule, the antiferromagnetic coupling represents the ground state for Mn(2)/GNR, and the spin density configuration of the GNR does not play an important role on the net magnetic moment of Mn(2), which makes GNRs an ideal substrate for adsorption of these molecules. The ground state and the excited state configuration of the Mn dimer, viz., low-spin (LS) and high-spin (HS), are maintained in the face of changes in the spin density configuration of the substrate. Here we find that the Mn(2)/GNR systems exhibit a LS <-> HS binary behavior, which can be considered as a useful property in the development of nanomemories based upon metallic clusters. (C) 2011 American Institute of Physics. [doi:10.1063/1.3553849]

Formation of atomic carbon chains from graphene nanoribbons

The formation of one-dimensional carbon chains from graphene nanoribbons is investigated using ab initio molecular dynamics. We show under what conditions it is possible to obtain a linear atomic chain via pulling of the graphene nanoribbons. The presence of dimers composed of two-coordinated carbon atoms at the edge of the ribbons is necessary for the formation of the linear chains, otherwise there is simply the full rupture of the structure. The presence of Stone-Wales defects close to these dimers may lead to the formation of longer chains. The local atomic configuration of the suspended atoms indicates the formation of single and triple bonds, which is a characteristic of polyynes.

Edge effects in bilayer graphene nanoribbons: Ab initio total-energy density functional theory calculations

We show that the ground state of zigzag bilayer graphene nanoribbons is nonmagnetic. It also possesses a finite gap, which has a nonmonotonic dependence with the width as a consequence of the competition between bulk and strongly attractive edge interactions. All results were obtained using ab initio total-energy density functional theory calculations with the inclusion of parametrized van der Waals interactions.

Electronic, structural, and transport properties of Ni-doped graphene nanoribbons

We have investigated the electronic and transport properties of zigzag Ni-adsorbed graphene nanoribbons (Ni/GNRs) using ab initio calculations. We find that the Ni adatoms lying along the edge of zigzag GNRs represent the energetically most stable configuration, with an energy difference of approximately 0.3 eV when compared to the adsorption in the middle of the ribbon. The carbon atoms at the ribbon edges still present nonzero magnetic moments as in the pristine GNR even though there is a quenching by a factor of almost five in the value of the local magnetic moments at the C atoms bonded to the Ni. This quenching decays relatively fast and at approximately 9 A from the Ni adsorption site the magnetic moments have already values close to the pristine ribbon. At the opposite edge and at the central carbon atoms the changes in the magnetic moments are negligible. The energetic preference for the antiparallel alignment between the magnetization at the opposite edges of the ribbon is still maintained upon Ni adsorption. We find many Ni d-related states within an energy window of 1 eV above and below the Fermi energy, which gives rise to a spin-dependent charge transport. These results suggest the possibility of manufacturing spin devices based on GNRs doped with Ni atoms.

Semiconducting Sn(3)O(4) nanobelts: Growth and electronic structure

The study of structures based on nonstoichiometric SnO(2-x) compounds, besides experimentally observed, is a challenging task taking into account their instabilities. In this paper, we report on single crystal Sn(3)O(4) nanobelts, which were successfully grown by a carbothermal evaporation process of SnO(2) powder in association with the well known vapor-solid mechanism. By combining the structural data and transport properties, the samples were investigated. The results showed a triclinic semiconductor structure with a fundamental gap of 2.9 eV. The semiconductor behavior was confirmed by the electron transport data, which pointed to the variable range hopping process as the main conduction mechanism, thus giving consistent support to the mechanisms underlying the observed semiconducting character.

Relationship between surface segregation and rapid propane electrical response in Cd-doped SnO2 nanornaterials

Controlling the surface properties of nanoparticles using ionic dopants prone to be surface segregated has emerged as an interesting tool for obtaining highly selective and sensitive sensors. In this work, the surface segregation of Cd cations on SnO2 nanopowders prepared by the Pechini`s method was studied by infrared spectroscopy, X-ray diffraction, and specific surface area analysis. We observed that the surface chemistry modifications caused by the surface segregation of Cd and the large specific surface area were closely responsible for a rapid and regular electrical response of 5 mol% Cd-doped SnO2 films to 100 ppm propane and NO, diluted in dry air at relatively low temperature (100 degrees C). (c) 2008 Elsevier B.V. All rights reserved.

Platinum nanoparticles embledded in layer-by-layer films from SnO2/polyallylamine for ethanol electrooxidation

Self-assembled films from SnO2 and polyallylamine (PAH) were deposited on gold via ionic attraction by the layer-by-layer(LbL) method. The modified electrodes were immersed into a H2PtCl6 solution, a current of 100 mu A was applied, and different electrodeposition times were used. The SnO2/PAH layers served as templates to yield metallic platinum with different particle sizes. The scanning tunnel microscopy images show that the particle size increases as a function of electrodeposition time. The potentiodynamic profile of the electrodes changes as a function of the electrodeposition time in 0.5 mol L-1 H2SO4, at a sweeping rate of 50mVs(-1). Oxygen-like species are formed at less positive potentials for the Pt-SnO2/PAH film in the case of the smallest platinum particles. Electrochemical impedance spectroscopy measurements in acid medium at 0.7 V show that the charge transfer resistance normalized by the exposed platinum area is 750 times greater for platinum electrode (300 k Omega cm(2)) compared with the Pt-SnO2/PAH film with 1 min of electrodeposition (0.4 k Omega cm(2)). According to the Langmuir-Hinshelwood bifunctional mechanism, the high degree of coverage with oxygen-like species on the platinum nanoparticles is responsible for the electrocatalytic activity of the Pt-SnO2/PAH concerning ethanol electrooxidation. With these features, this Pt-SnO2/PAH film may be grown on a proton exchange membrane (PEM) in direct ethanol fuel cells (DEFC). (c) 2008 Elsevier B.V. All rights reserved.

Structural, electrical and magnetic studies of Co:SnO2 and (Co,Mo):SnO2 films prepared by pulsed laser deposition

Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 degrees C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the [1 0 1] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis of Sub-5 NM Co-Doped SnO2 nanoparticles and their structural microstructural, optical and photocatalytic properties

A swift chemical route to synthesize Co-doped SnO2 nanopowders is described. Pure and highly stable Sn1-xCoxO2-delta (0 <= x <= 0.15) crystalline nanoparticles were synthesized, with mean grain sizes <5 nm and the dopant element homogeneously distributed in the SnO2 matrix. The UV-visible diffuse reflectance spectra of the Sn1-xCoxO2-delta samples reveal red shifts, the optical bandgap energies decreasing with increasing Co concentration. The samples' Urbach energies were calculated and correlated with their bandgap energies. The photocatalytic activity of the Sn1-xCoxO2-delta samples was investigated for the 4-hydroxylbenzoic acid (4-HBA) degradation process. A complete photodegradation of a 10 ppm 4-HBA solution was achieved using 0.02% (w/w) of Sn0.95Co0.05O2-delta nanoparticles in 60 min of irradiation. (C) 2014 Elsevier B.V. All rights reserved.

Ab initio study of NOx compounds adsorption on SnO2 surface

An ab initio study of the adsorption processes on NOx compounds on (1 1 0) SnO2 surface is presented with the aim of providing theoretical hints for the development of improved NOx gas sensors. From first principles calculations (DFT¿GGA approximation), the most relevant NO and NO2 adsorption processes are analyzed by means of the estimation of their adsorption energies. The resulting values and the developed model are also corroborated with experimental desorption temperatures for NO and NO2, allowing us to explain the temperature-programmed desorption experiments. The interference of the SO2 poisoning agent on the studied processes is discussed and the adsorption site blocking consequences on sensing response are analyzed.

Nanocrystalline SnO2 by liquid pyrolisis

Liquid pyrolysis is presented as a new production method of SnO2 nanocrystalline powders suitable for gas sensor devices. The method is based on a pyrolytic reaction of high tensioned stressed drops of an organic solution of SnCl4·5(H2O). The main advantages of the method are its capability to produce SnO2 nanopowders with high stability, its accurate control over the grain size and other structural characteristics, its high level of repeatability and its low industrialization implementation cost. The characterization of samples of SnO2 nanoparticles obtained by liquid pyrolysis in the range between 200ºC and 900ºC processing temperature is carried out by X-ray diffraction, transmission electron microscopy, Raman and X-ray photoelectron spectroscopy. Results are analyzed and discussed so as to validate the advantages of the liquid pyrolysis method.

Defect study of SnO2 nanostructures by cathodoluminescence analysis: Application to nanowires

Defects in SnO2 nanowires have been studied by cathodoluminescence, and the obtained spectra have been compared with those measured on SnO2 nanocrystals of different sizes in order to reveal information about point defects not determined by other characterization techniques. Dependence of the luminescence bands on the thermal treatment temperatures and pre-treatment conditions have been determined pointing out their possible relation, due to the used treatment conditions, with the oxygen vacancy concentration. To explain these cathodoluminescence spectra and their behavior, a model based on first-principles calculations of the surface oxygen vacancies in the different crystallographic directions is proposed for corroborating the existence of surface state bands localized at energy values compatible with the found cathodoluminescence bands and with the gas sensing mechanisms. CL bands centered at 1.90 and 2.20 eV are attributed to the surface oxygen vacancies 100° coordinated with tin atoms, whereas CL bands centered at 2.37 and 2.75 eV are related to the surface oxygen vacancies 130° coordinated. This combined process of cathodoluminescence and ab initio calculations is shown to be a powerful tool for nanowire defect analysis.