Oxygen-doped boron nitride nanosheets with excellent performance in hydrogen storage

Hydrogen is considered one of the best energy sources. However, the lack of effective, stable, and safe storage materials has severely prevented its practical application. Strong effort has been made to try new nanostructured materials as new storage materials. In this study, oxygen-doped boron nitride (BN) nanosheets with 2-6 atomic layers, synthesized by a facile sol-gel method, show a storage capacity of 5.7wt% under 5MPa at room temperature, which is the highest hydrogen storage ever reported for any BN materials. Importantly, 89% of the stored hydrogen can be released when the hydrogen pressure is reduced to ambient conditions. Furthermore, the BN nanosheets exhibit an excellent storage cycling stability due to the stable two-dimensional nanostructure. The first principles calculations reveal that the high hydrogen storage mainly origins from the oxygen-doping of the BN nanosheets with increased adsorption energies of H2 on BN by 20-80% over pure BN sheets at the different coverage. © 2014 Elsevier Ltd.

Selective UV-filter detection with sensors based on stainless steel electrodes modified with polyaniline doped with metal tetrasulfonated phthalocyanine films

This work describes the construction and application of two amperometric sensors for sensitive UV-filter determination. The sensors were prepared using stainless steel electrodes in which polyaniline (PANI) was electrochemically polymerized in the presence of nickel (NiPcTS) or iron (FePcTS) tetrasulfonated phthalocyanines. The sensor surface characterizations were carried out using atomic force microscopy (AFM). The PANI/NiPcTS sensor was selective for the chemical UV-filter p-aminobenzoic acid (PABA) and the PANI/FePcTS sensor was selective for octyldimethyl-PABA (ODP), both in a mixture of tetrahydrofuran (THF) and 0.1 mol L(-1) H(2)SO(4) at a volume ratio of 30 : 70, and with an applied potential of 0.0 mV vs. Ag vertical bar AgCl. A detailed investigation of the selectivity was carried out for both sensors, in order to determine their responses for ten different UV filters. Finally, each sensor was successfully applied to PABA or ODP quantification in sunscreen formulations and water from swimming pools.

Charge carrier exchange at chemically modified graphene edges: A density functional theory study

Heteroatom doping on the edge of graphene may serve as an effective way to tune chemical activity of carbon-based electrodes with respect to charge carrier transfer in an aqueous environment. In a step towards developing mechanistic understanding of this phenomenon, we explore herein mechanisms of proton transfer from aqueous solution to pristine and doped graphene edges utilizing density functional theory. Atomic B-, N-, and O- doped edges as well as the native graphene are examined, displaying varying proton affinities and effective interaction ranges with the H3O+ charge carrier. Our study shows that the doped edges characterized by more dispersive orbitals, namely boron and nitrogen, demonstrate more energetically favourable charge carrier exchange compared with oxygen, which features more localized orbitals. Extended calculations are carried out to examine proton transfer from the hydronium ion in the presence of explicit water, with results indicating that the basic mechanistic features of the simpler model are unchanged.

Multi-wall carbon nanotube coating of fluorine-doped tin oxide as an electrode surface modifier for polymer solar cells

A controlled layer of multi-wall carbon nanotubes (MWCNT) was grown directly on top of fluorine-doped tin oxide (FTO) glass electrodes as a surface modifier for improving the performance of polymer solar cells. By using low-temperature chemical vapor deposition with short synthesis times, very short MWCNTs were grown, these uniformly decorating the FTO surface. The chemical vapor deposition parameters were carefully refined to balance the tube size and density, while minimizing the decrease in conductivity and light harvesting of the electrode. As created FTO/CNT electrodes were applied to bulk-heterojunction polymer solar cells, both in direct and inverted architecture. Thanks to the inclusion of MWCNT and the consequent nano-structuring of the electrode surface, we observe an increase in external quantum efficiency in the wavelength range from 550 to 650 nm. Overall, polymer solar cells realized with these FTO/CNT electrodes attain power conversion efficiency higher than 2%, outclassing reference cells based on standard FTO electrodes.

Highly NO2 sensitive caesium doped graphene oxide conductometric sensors

Here we report on the synthesis of caesium doped graphene oxide (GO-Cs) and its application to the development of a novel NO2 gas sensor. The GO, synthesized by oxidation of graphite through chemical treatment, was doped with Cs by thermal solid-state reaction. The samples, dispersed in DI water by sonication, have been drop-casted on standard interdigitated Pt electrodes. The response of both pristine and Cs doped GO to NO2 at room temperature is studied by varying the gas concentration. The developed GO-Cs sensor shows a higher response to NO2 than the pristine GO based sensor due to the oxygen functional groups. The detection limit measured with GO-Cs sensor is ≈90 ppb.

On natures of sub-gap photoelectric and optical spectra in nitrogen-contaminated nanocrystalline diamond

Experimentally observed optical and photoelectrical spectra of nitrogen-contaminated (unintentionally doped) nano-crystalline CVD diamond films are simulated using semi-empirical adiabatic General Skettrup Model (GSM), which presumes dominant contributions of defect states from sp 3-coordinated intra-granular carbon atoms to intra-band single electron spectrum N(E) of the material. This picture disagrees with a common viewpoint that the N(E) spectrum of the gap states in diamond powders and polycrystalline CVD films mainly originates from π and π* bonds of sp2-coordinated carbon atoms, which are distributed nearly uniformly over outer surfaces and/or interfaces of the diamond grains. The GSM predicts as well strong effect of granular morphology on the density of intra-band defect states in polycrystalline diamonds.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: Influence of process parameters on the electrical and optical properties

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp2 carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 105 S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Fabrication of Fe-doped WO3 films for NO2 sensing at lower operating temperature

Fe-doped tungsten oxide thin films with different concentrations (0 to 2.6 at%) were synthesized on glass and alumina substrates at room temperature using DC reactive sputtering and subsequently annealed at 300oC for 1 hour in air. The alumina substrate has pre-printed interdigitated Pt-electrodes for gas sensing measurements. The effects of Fe-doping on the film structure and morphology, electronic and optical properties for gas sensing were investigated. The grain size of the different films on the alumina and Pt regions of the substrate vary only slightly between 43-57 nm with median size of about 50 nm. Raman spectra showed that the integrated intensity of W=O to O–W–O bands increases with increasing Fe concentrations and this indicated an increase in the number of defects. From XPS the different concentrations of the Fe-doped films were 0.03 at%, 1.33 at% and 2.6 at%. All the films deposited on glass substrate have shown similar visible transmittance (about 70%) but the optical band gap of the pure film decreased form 3.30 eV to 3.15 eV after doping with 2.6 at% Fe. The Fe-doped WO3 film with the highest Fe concentration (2.6 at% Fe) has shown an enhanced gas sensing properties to NO2 at relatively lower operating temperature (150oC) and this can be attributed to the decrease in the optical band gap and an increase in the number of defects compared to the pure WO3 film.

Characteristics of field-effect transistors based on undoped and B-and N-doped few-layer graphenes

Field-effect transistor characteristics of few-layer graphenes prepared by several methods have been investigated in comparison with those of single-layer graphene prepared by the in situ reduction of single-layer graphene oxide. Ambipolar features have been observed with single-layer graphene and n-type behaviour with all the few-layer graphenes, the best characteristics being found with the graphene possessing 2-3 layers prepared by arc-discharge of graphite in hydrogen. FETs based on boron and nitrogen doped graphene show n-type and p-type behaviour respectively. (C) 2010 Elsevier Ltd. All rights reserved.

Novel Nanocomposites Made of Boron Nitride Nanotubes and a Physical Gel

This article describes successful incorporation of multiwalled boron nitride nanotubes (BNNTs) and various functionalized BNNTs by Lewis bases such as trioctylamine (TOA), tributylamine (TBA), and triphenylphosphine (TPP), etc., in organogels formed by triphenylenevinylene (TPV)-based low molecular weight gelator (LMWG) in toluene and consequent characterization of the resulting gel nanocomposites. Functionalized BNNTs were synthesized first,and the presence of tubular structures with high aspect ratio and increased diameter compared to the starting BNNTs was confirmed by SEM. TEM, and Raman spectroscopy. The micrographs of composites of I and BNNTs showed evidence of wrapping of the gelator molecules on to the BNNT surface presumably brought about by pi-pi stacking and van der Waals interactions, This leads to the formation of densely packed and directionally aligned fibrous networks. Such ``reinforced'' aggregation of the gelator molecules in presence of doped BNNTs led to an increase in the sot-to-gel transition temperature and the solidification temperature of the gel nanocomposites as revealed from differential scanning calorimetry. Rheological investigations of the gel nanocomposites indicate that the flow properties of the resulting materials become resistant to applied stress upon incorporation of even a very low wt % of BNNTs. Finally, the increase in thermal conductivity of the nanocomposite compared to the gelator alone was observed for the temperature range of 0-60 degrees C which may make these composites potentially useful in various applications depending on the choice and the amount of BNNT loading in the composite.

Transport and magnetic properties of conducting polyaniline doped with BX3 (X=F, Cl, and Br)

We report transport and magnetic properties of a different class of highly conducting polyaniline, doped with boron trihalides BX3 (X=F, Cl, and Br). In order to understand the transport mechanism we analyze the temperature dependence of resistivity of a large number of samples, made by pelletizing doped polyaniline powder and by doping films of polyaniline. We find that the charge transport in this class of conducting polyaniline is driven by the charging-energy limited transport of charge carriers, in contrast to the quasi-one-dimensional variable range hopping conduction prevalent in conventional proton-doped polyaniline samples. Magnetic susceptibility provides further insight into the unusually high intrinsic conductivity behavior.

Gradient solid-electrolyte for use with dissimilar gas electrodes

The EMF of a solid-state cell, incorporating a composite solid-electrolyte with gradual variation in composition, and dissimilar gas electrodes, has been studied as a function of temperature and partial pressures at the electrodes. The cell with the configuration: Pt, CO2' + O2' parallel-to Na2CO3\Na(SO4)x(CO3)1-x\Na2SO4 parallel-to SO3'' + SO2'' + O2'', Pt x=0 x=1 was investigated in the temperature range 973 to 1079 K. The solid-electrolyte surface exposed to SO3 + SO2 + O2 gas mixture was doped-Na2SO4, whereas the CO2 + O2 gas mixture was in contact with pure Na2CO3. The composition of the solid solution between the carbonate and sulfate, with hexagonal structure, was varied gradually between the boundary values. It has been found that the EMF of the cell is close to that calculated from thermodynamic data, assuming unit transport number for Na+ ions. The gradient in the concentration of sulfate and carbonate ions in the electrolyte does not give rise to a significant diffusion potential.

Structural ordering of diamond like carbon films by applied electric field

Diamond like carbon films deposited by RF magnetron sputter deposition technique contain both SP2 and SP3 hybridized carbons. These films are structurally disordered and inhomogeneous. By the application of electric field across the film, these films are transformed to a more orderly structured diamond like carbon, bringing homogenity in the film. This transformation has resulted in the increase of the reflectivity of the metal(Aluminum), which is used as one of the electrodes for applying the electric field, by 5 times.

A Raman study of the interaction of electron-donor and -acceptor molecules with chemically doped graphene

Effect of interaction of tetracyanoethylene (TCNE) and tetrathia fulvalene (TTF) with boron- and nitrogen-doped graphene has been investigated by Raman spectroscopy. The G- and 2D bands of boron- and nitrogen-doped graphenes in the Raman spectra show significantly different changes on interaction with electron-donor and -acceptor molecules. Thus, tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) have different effects on the Raman spectra of boron- and nitrogen-doped graphenes. The changes in the Raman spectra brought about by electron-donor and -acceptor molecules can be understood in general terms on the basis of molecular charge transfer. (c) 2012 Elsevier B.V. All rights reserved.