The effect of vacuum annealing on graphene

The effect of vacuum annealing on the properties of graphene is investigated by using Raman spectroscopy and electrical measurement. Heavy hole doping on graphene with concentration as high as 1.5 × 10¹³ cm⁻² is observed after vacuum annealing and exposed to an air ambient. This doping is due to the H₂O and O₂ adsorption on graphene, and graphene is believed to be more active to molecular adsorption after annealing. Such observation calls for special attention in the process of fabricating graphene‐based electronic devices and gas sensors. On the other hand, because the quality of graphene remains high after the doping process, this would be an efficient and controllable method to introduce heavy doping in graphene, which would greatly help on its application in future electronic devices. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and gas sensing properties of perovskite CdSnO<Subscript>3</Subscript> nanoparticles

The CdSnO₃ semiconducting oxide that can be used as a gas-sensitive material for detecting ethanol gas is reported in this paper. CdSnO₃ nanoparticles were prepared by a chemical co-precipitation synthesis method, in which the preparation conditions were carefully controlled. The n-type gas-sensing semiconductors were obtained from the as-synthesized powders calcined at 600°C for 1 h. The phase and microstructure of the obtained nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET) method with a gas adsorption analyzer. CdSnO₃ has a small particle size range of 30–50 nm and a high surface area of 9.12 m²/g, and a uniformity global shape. The gas sensitivity and operating temperature, and selectivity of CdSnO₃-based sensors were measured in detail. The gas sensors fabricated by CdSnO₃ nanoparticles had good sensitivity and selectivity to vapor of C₂H₅OH when working temperature at 267°C, the value of gas sensitivity at 100 ppm of C₂H₅OH gas can reach 11.2 times. Furthermore, gas-sensing mechanism was studied by using chromatographic analysis.     

Two-step method preparation of graphene without hydrogen on methanol pretreatment copper substrate by PECVD at low temperature

Plasma enhanced chemical vapor deposition (PECVD) is one effective method to prepare graphene at low temperature in a short time. However, the low temperature in PECVD could not provide substrate a proper state for large area and few layer graphene preparation. Herein, we propose a two-step method to grow graphene on Cu foils. In the first step, in order to acquire a smooth and oxide-free surface state, methanol was used as a reductant to pretreat Cu. In the second step, graphene films were prepared on Cu foils by PECVD using CH₄ as carbon source with H₂-free. Few-layer graphene sheets with diameter about 1 μm under low temperature (700 °C) and at a short time (10 min) on well pretreated Cu foils were successfully gotten. The effect of methanol pretreatment on graphene synthesis and the graphene growth mechanism on Cu substrate by PECVD are analyzed comprehensively.     

Reactions and anion desorption induced by low-energy electron exposure of condensed acetonitrile

Thermal desorption spectrometry (TDS) and electron stimulated desorption (ESD) are employed to investigate mechanisms responsible for the formation of C₂H₆ in electron irradiated multilayer films of acetonitrile (CH₃CN) at 30 K. Using a high sensitivity time-of-flight mass spectrometer, we observe the ESD of anionic fragments H⁻, CH₂ ⁻, CH₃ ⁻ and CN⁻. Desorption occurs following dissociative electron attachment (DEA) via several negative ion resonances in the 6 to 14 eV energy range and correlates well with a “resonant” structure seen in the TDS yield of C₂H₆ (i.e., at mass 30 amu). It is proposed that C₂H₆ is formed by the reactions of CH₃ radicals generated following DEA to CH₃CN which also yields CN⁻. Between 2 and 5 eV, a second resonant feature is seen in the C₂H₆ signal. While DEA is observed in the gas phase at these energies, no anion desorption occurs since anionic fragments likely have insufficient kinetic energy to desorb. Since the CH₂ ⁻ ion has not been observed in gas-phase measurements, we propose that it is formed, along with HCN (that is detected in TDS) when dissociation into CH₃ ⁻ and CN is hindered by adjacent molecules.     

Growth, microhardness, dielectric and photoconductivity characterization of a highly polarizable NLO material: Sodium p-nitrophenolate dihydrate (NO2-C6H4-ONa.2H2O)

Sodium p-nitrophenolate dihydrate (NPNa.2H₂O) is a highly polarisable non linear optical material. It has a d_eff about 1.45 times than that of potassium titanyl phosphate. Single crystals of (NPNa.2H₂O) have been grown successfully by slow solvent evaporation having water and methanol as solvent. The structure of the crystal is verified by single X-ray analysis. Optical absorption shows that the crystal is highly transparent between 1500 and 300 nm. Microhardness of the crystal is found to increases with increase in load and the hardness number is found to be high for methanol grown crystal as compared to the water grown crystal. Electrical conductivity as evaluated from the cole-cole plot is found to be 1.26 × 10⁻⁵ mho m⁻¹. The dielectric constant of the crystal is low and independent at higher frequencies. The crystal has prominent photoconduction in the presence of trap energy levels formed by the Na⁺ ions. The SHG efficiency of the crystal is studied by performing Kurtz powder test and the results of scanning electron microscope analysis indicate that the major part of the crystal surface is free from inclusion and dislocation.     

A model of single-electron transport. Calculation of the thermodynamic parameters for electron capture by the bound proton of oxyacids

Electron transfer is an elementary chemical event involved in many biochemical reactions. Experiments have shown that some oxyacids participating in electron transport are capable of dissociative capture of low-energy electrons, a process indicative of the formation of a metastable anion. The present work reports the results of quantum-chemical simulations of the dissociative electron attachment to a number of oxyacids (H₃PO₄, H₂SO₄⁻, HPO₄²⁻, H₂SO₄, HSO₄⁻, B(OH)₄⁻, HCOOH) with formation of a hydrogen atom in vacuum and in the aqueous medium. Phosphate is one of the most important building units of biological molecules, whereas formic acid can serve as a model of the −COOH group in amino acids, carboxylic acids, functional sites of enzymes, etc. The electron affinity of these oxyacids in the aquatic environment is positive and exceeds the energy of hydrogen atom abstraction. The proton of the OH group captures the electron, while the aquatic environment stabilizes it in the trapped state due to its polarizability. The data obtained provide a fresh look at the phenomenon of proton-assisted electron transfer and at the use of oxyacid buffers.     

In situ investigation of the catalytic reaction H2+< ![IGNORE[O2→H2 O with second-harmonic generation

2 +O₂→H₂ O in the pressure range 0.2 Torr≤p_tot≤10 Torr on Pt(111) surface. At a catalyst temperature of T=700 K the equilibrium oxygen coverage θ_o is determined as a function of hydrogen partial pressure α. The experimentally obtained θ_o is modelled in a two step process considering the mass transport in the gas phase as well as the catalytic reaction on the surface. In this pressure range the mass transport in the gas phase changes from molecular flow conditions to laminar flow, inducing a strong modification of the gas phase present at the catalyst through different diffusivities of the reactants as well as through desorbing reaction products from the catalyst. It is shown that these gas phase alterations have to be taken into account for a proper modelling of the surface mechanism. Simulation calculations allow one to identify the sequential hydrogen addition reaction as the main reaction path for water production in this parameter range. Excellent agreement with previous investigations is obtained for the determined activation energies of the water-producing reaction steps equal to E^f _H2O≥0.7 eV. Received: 20 September 1998 / Revised version: 15 December 1998     

Cross-section and rate coefficient calculation for electron impact excitation, ionisation and dissociation of H2 and OH molecules

The weighted total cross-section (WTCS) theory is used to calculate electron impact excitation, ionisation and dissociation cross-sections and rate coefficients of OH, H₂, OH⁺, H₂ ⁺, OH^- and H₂ ^- diatomic molecules in the temperature range 1500–15000 K. Calculations are performed for H₂(X, B, C), OH(X, A, B), H₂ ⁺(X), OH⁺(X, a, A, b, c), H₂ ^-(X) and OH^-(X) electronic states for which Dunham coefficients are available. Rate coefficients are calculated from WTCS assuming Maxwellian energy distribution functions for electrons and heavy particles. One and two temperature (θ_e and θ_g respectively for electron and heavy particles kinetic temperatures) results are presented and fitting parameters (a, b and c) are given for each reaction rate coefficient: k(θ) = a (θ^b)exp (-c/θ).     

Synthesis and characterization of α-cobalt hydroxide nanobelts

α-Cobalt hydroxide was synthesized by a facile hydrothermal process from Co(Ac)₂ and NH₃·H₂O in the presence of 1,3-propanediol. The large-scale-prepared cobalt hydroxide has a uniform nanobelt morphology with a considerably high aspect-ratio more than 20 which may be advantageous for exploration of their physicochemical properties. This synthetic method is convenient, economical, and controllable. The samples were characterized by powder X-ray diffraction, energy dispersive spectrum, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, CHN element analysis, thermogravimetric and differential-thermogravimetric analysis, which revealed the compound is lamellar structural cobalt organic–inorganic hybrid with the chemical formula of Co(OH)_1.49(NH₃)_0.01(CO₃ ²⁻)_0.22(Ac⁻)_0.07(H₂O)_0.11 and single-crystalline.     

Fragmentation of the POPOP molecule by electron-impact ionization

Single and dissociative ionizations of the POPOP molecule by electron impact in the gas phase are studied using mass spectroscopy. Fragmentation pathways of the molecule are proposed taking into account the common system of conjugated π-electrons and heteroatoms in the POPOP molecule. The appearance thresholds for certain fragments of the molecule are determined based on experimentally measured ionization cross sections as functions of the ionizing electron energy. An ion with m/z = 144 [C₉H₆ON]⁺ that is complementary to a fragment with m/z = 220 [C₁₃H₁₀ON]⁺ (present in the NIST mass spectrum database) is found for the first time in the mass spectrum of POPOP. Its appearance threshold is determined (E_ap = 9.48 eV). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 482–489, July–August, 2008.     

Kinetics of the formation of gas bubbles during polarization of copper and graphite electrodes in electrolytic aqueous solutions

The adsorption and kinetic processes of the formation of gas bubbles passivating the surface during polarization of copper and graphite electrodes in 1% aqueous solution of sulfuric acid have been investigated. Three stages of the process related to the recharging of the double electric layer—adsorption accumulation of the gas escaping from the surface, the critical nucleation of the gas bubbles, and their subsequent growth—have been revealed, distinguished, and quantitatively estimated. It has been shown that potential leveling at the steady-state value specified by the Tafel equation is unambiguously associated with achievement of the limiting surface area screened by the gas bubbles for each particular current density. The surface diffusion constants D _H = (1.5–4.4) × 10⁻⁴ and (0.1–3.8) × 10⁻⁵ cm²/s of hydrogen on copper and graphite, respectively, and D _O = (1.8–4.5) × 10⁻⁷ cm²/s of oxygen on graphite during the motion toward the drain (the gas bubbles) have been calculated.     

Raman imaging on high‐quality graphene grown by hot‐filament chemical vapor deposition

We report the synthesis of high‐quality graphene on Cu foils using hot‐filament chemical vapor deposition technique and demonstrate that by suitably varying the CH₄ and H₂ flow rates, one can also obtain hydrogenated graphene. Micro‐Raman spectroscopy studies confirm the growth of monolayer graphene as inferred from the intensity ratio of 2D to G peak which is nearly four in unhydrogenated samples. Detailed Raman area mapping confirms the uniform coverage of monolayer graphene. The grown layer is also transferred onto a Si substrate over ~10 × 10 mm sq. area. The present results provide a leap in synthesis technology of high‐quality graphene and pave way for scaling up the process. Copyright © 2012 John Wiley & Sons, Ltd.     

Dissociative electron attachment to the explosive detection taggant 2,3-dimethyl-2,3-dinitrobutane (DMNB)

A detailed study on dissociative electron attachment (DEA) to 2,3-dimethyl-2,3-dinitrobutane (DMNB) in the gas phase is presented. Ion yields as a function of the incident electron energy from about 0 to 14 eV have been measured for the most dominant fragments including anions such as NO₂ ⁻, [M-NO₂]⁻ or N₂O₄ ⁻. To help identifying which anion and neutral fragments are formed upon electron attachment we calculated the thermodynamic thresholds using the G4(MP2) method.     

Near-infrared laser based cavity ringdown spectroscopy for applications in petrochemical industry

A simple, economic diode laser based cavity ringdown system for trace-gas applications in the petrochemical industry is presented. As acetylene (C₂H₂) is sometimes present as an interfering contaminant in the gas flow of ethylene (ethene, C₂H₄) in a polyethylene production process, an on-line monitoring of such traces is essential. We investigated C₂H₂–C₂H₄ mixtures in a gas-flow configuration in real time. The experimental setup consists of a near-infrared external cavity diode laser with an output power of a few mW, standard telecommunication fibers and a home-made gas cell providing a user-friendly cavity alignment. A noise-equivalent detection sensitivity of 4.5×10^-8 cm^-1 Hz^-1/2 was achieved, corresponding to a detection limit of 20 ppbV C₂H₂ in synthetic air at 100 mbar. In an actual C₂H₂–C₂H₄ gas-flow measurement the minimum detectable concentration of C₂H₂ added to the C₂H₄ gas stream (which may already contain an unknown C₂H₂ contamination) increased to 160 ppbV. Moreover, stepwise C₂H₂ concentration increments of 500 ppbV were resolved with a 1-min time resolution and an excellent linear relationship between the absorption coefficient and the concentration was found. PACS 07.07.Df; 42.62.Fi; 82.80.Gk     

A parametric study of the synthesis and purification of single-walled carbon nanotubes using the high-pressure carbon monoxide process

Single-walled carbon nanotubes (SWCNTs) were synthesized using the high-pressure carbon monoxide disproportionation process. The SWCNT diameter, diameter distribution and yield can be varied depending on the process parameters. Important parameters are the temperature, the pressure, the CO gas flow rate and the nozzle injection velocity and geometry for the injection of reactant gas into the reaction zone. Carbon nanotubes as small as 1.0 nm in diameter have been produced. The purity and yield of the deposited material were increased with increasing CO gas flow by means of rapid heating of the gas mixture and using an optimum injection profile. Highly pure SWCNTs were produced at 1250 K, pressures between 5 and 10 bar and gas in the turbulent flow regime in the cold line of 2000–2500 sccm CO. The raw materials were purified by oxidation in high vacuum at 523 K in wet Ar/20 vol. % O₂ to remove SWCNT carbon-like impurities and to oxidize the iron catalyst nanoparticles. The iron oxides were removed by chemical treatment in concentrated HCl/C₂H₅OH mixture solution. The SWCNTs were analyzed by scanning electron microscopy, high-resolution transmission electron microscopy, atomic absorption spectroscopy and optical absorption spectroscopy to determine the purity, the diameter and diameter distribution, the chemical composition and the catalyst morphology, as well as the optical properties of deposited SWCNTs in dependence on the synthesis parameters. PACS 29.30.-h     

Multiwalled carbon nanotubes mass-produced by dc arc discharge in He–H2 gas mixture

Uniform cathode deposits (longer than 15 mm), containing multiwalled carbon nanotubes (MWNTs) inside, were produced by dc arc discharge evaporation with a computer-controlled feeder of a pure-carbon electrode without a metal catalyst in a He–H₂ gas mixture. The purification of MWNTs was carried out to remove amorphous carbon and carbon nanoparticles. High-resolution transmission electron microscopy observations and Raman scattering studies show that the MWNTs possess a high crystallinity and a mean outermost diameter of ∼ ∼10 nm. It has been confirmed that the current density in the electron field emission from a purified MWNT mat can reach 77.92 mA/cm², indicating that the purified MWNTs are a promising candidate electron source in a super high-luminance light-source tube or a miniature X-ray source.     

A facile and one pot synthesis of 1,4-disubstituted-1H-1,2,3-triazoles from terminal alkynes and phenacyl azides prepared from styrenes by CAN oxidant and sodium azide

A facile and green synthesis of 1,4-disubstituted-1H-1,2,3-triazoles is reported. The reaction of α-azido ketones and terminal alkynes in the presence of [CuSO₄ (H₂O)₅/sodium ascorbate] in a mixture of H₂O/polyethylene glycol 400 as solvent afforded the corresponding 1,4-disubstituted triazoles at ambient temperature with short reaction times and at high yields. The corresponding α-azido ketones were directly prepared in situ from various substituted styrenes using the oxidant cerium ammonium nitrate and sodium azide in oxygen-saturated methanol.     

Impact of water vapor on 1.51 μm ammonia absorption features used in trace gas sensing applications

Water-vapor-induced pressure broadening is reported for two NH₃ absorption features at 6612.7 and 6596.4 cm⁻¹ that are exploitable for gas sensing applications at atmospheric pressure. Absorption spectra of different NH₃–H₂O–N₂ mixtures were measured at an elevated temperature of 70°C to enable high H₂O concentrations to be reached. Line parameters were determined from a fitting procedure. The significantly greater values obtained for the H₂O-broadening coefficients of the two lines compared to N₂-broadening leads to cross-sensitivity effects in NH₃ trace gas sensors based on spectroscopic techniques that are sensitive to the width of the analyzed absorption line, as is the case in a simple implementation of wavelength modulation spectroscopy or in photoacoustic spectroscopy. In such a case, cross-sensitivity results in inaccurate gas concentration retrieval when the composition of the diluting gas changes. H₂O represents a potentially significant cross-sensitivity source as its concentration may be subject to large variations, especially in high-temperature applications where concentrations up to a couple of tens of percent may be encountered. In contrast to interference which can be minimized by an appropriate choice of the analyzed transitions, cross-sensitivity affects the entire spectrum of the analyte and is thus unavoidable in the mentioned type of gas sensors.     

Reductive Fluorescence Quenching of the Photoexcited Free Base <Emphasis Type="Italic">meso</Emphasis>-Tetrakis (Pentafluorophenyl) Porphyrin by Amines

Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H₂F₂₀TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H₂F₂₀TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime τ _f = 9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H₂F₂₀TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H₂F₂₀TPP. The fluorescence quenching rate constants ranged from 1 × 10⁹ to 4 × 10⁹ s⁻¹, which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern–Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H₂F₂₀TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (∆G⁰) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.     

High hydrogen-storage capacity of B-adsorbed graphene: First-principles calculation

Based on density functional calculations, boron-adsorbed graphene has  been found to be a kind of hydrogen-storage medium. B-adsorbed graphene has excellent hydrogen-storage capacity: when the B atoms are adsorbed on one side, the hydrogen-storage capacity is up to 10.10 wt% and when the adsorption is on both sides the capacity is up to 16.95 wt%. In each of these two cases, the hydrogen-storage capacity exceeds 6 wt%, surpassing the target of US Department of Energy (DOE). The calculated adsorption energy of H₂ molecules is ?0.209 eV/H₂ and ?0.208 eV/H₂ for single-side and both-sides B-adsorbed graphene, respectively, which is within the range ?0.2 to ?0.6 eV/H₂ and indicates that hydrogenous storage can be recycled in near ambient conditions. By analyzing the electron density distribution of the adsorbed system, we have found that the high hydrogen-storage capacity was due to the change of electron distribution of H₂ molecules and graphene by adsorbed B atoms.