2012 Vol. 25, No. 4

2012, 25(4): 0-0. doi: 10.1088/1674-0068/25/4/0-0
The photodissociation dynamics of 2-bromobutane has been investigated at 264.77 and 264.86 nm by ion-velocity map imaging technique coupled with resonance-enhanced multi-photon ionization. The speed and angular distributions have been derived from the velocity map images of Br and Br*. The speed distributions of Br and Br* atoms in the photodis-sociation of 2-bromobutane at ~265 nm can be fitted using only one Gaussian function indicating that bromine fragments were produced via direct dissociation of C-Br bond. Thecontributions of the excited 3Q0, 3Q1, and 1Q1 states to the products (Br and Br*) were discussed. It is found that the nonadiabatic 1Q13Q0 transition plays an important role for Br photofragment in the dissociation of 2-C4H9Br at ~265 nm. Relative quantum yield of 0.621 for Br(2P3/2) at ~265 nm in the photodissociation of 2-bromobutane is derived. By comparing the photodissociation of 2-C4H9Br at ~265 nm and that that at ~234 nm, the anisotropy parameter β(Br) and β(Br*), and relative quantum yield ?(Br) decrease with increasing wavelength, the probability of curve crossing between 3Q0 and 1Q1 decreases with increasing laser wavelength.
Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi-gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal-culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization e±ciency curves, appearance energies for the principal fragment ions C5H12N+ (m/z=86)、C2H5NO4+ (m/z=75)、C5H9+ (m/z=69)、C4H9+(m/z=57), and CH4N+(m/z=30) are determined to be 8.84±0.07, 9.25±0.06, 10.20±0.12, 9.25±0.10, and 11.05±0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31++G(d, p) levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.
The coil-to-globule transition of thermally sensitive linear poly(N-isopropylacrylamide) (PNIPAM) labeled with dansyl group is induced by 1.54 μm laser pulses (width≈10 ns). The dansyl group is used to follow the transition kinetics because its fluorescence intensity is very sensitive to its micro-environment. As the molar ratio of NIPAM monomer to dansyl group increases from 110 to 300, the effect of covalently attached dansyl fluorophores on the transition decreases. In agreement with our previous study in which we used 8-anilino-1-naphthalensulfonic acid ammonium salt free in water as a fluorescent probe, the current study reveals that the transition has two distinct stages with two characteristic times, namely, τfast≈0.1 ms, which can be attributed to the nucleation and formation of some "pearls" (lo-cally contracting segments) on the chain, and τslow≈0.5 ms, which is related to the merging and coarsening of the "pearls". τfast is independent of the PNIPAM chain length over a wide range (Mw=2.8×106-4.2×107 g/mol). On the other hand, τslow only slightly increases with the chain length.
The conformations for leucine (Leu) hydrated with one to three water molecules, Leu-(H2O)n (n=1-3), were carefully searched by considering the trial structures generated by all possible combinations of rotamers of Leu combined with all likely hydration modes. The structures were optimized at the BHandHLYP/6-31+G* level and the single point energies were calcu-lated at the BHandHLYP/6-311++G** level. Good correspondence between the conforma-tions of Leu-(H2O)n and bare Leu is found, showing that the conformations of Leu-(H2O)nmay be effciently and reliably determined by the hydration of Leu conformers. The simu-lated IR spectra of canonical and zwitterionic conformers of Leu-(H2O)n are compared with the experimental result of Leu in aqueous solution. The IR spectrum of zwitterionic Leu-(H2O)3 provides the best description of the experiment. The result demonstrates that the IR spectrum of solute in solution may be simulated by the solute hydrated with an adequate number of water molecules in the gas phase.
We have studied the nucleation process of a two-dimensional kinetic Ising model subject to a bias oscillating external field, focusing on how the nucleation time depends on the oscillation frequency. It is found that the nucleation time shows a clear-cut minimum with the variation of oscillation frequency, wherein the average size of the critical nuclei is the smallest, indicating that an oscillating external field with an optimal frequency can be much more favorable to the nucleation process than a constant field. We have also investigated the effect of the initial phase of the external field, which helps to illustrate the occurrence of such an interesting finding.
The adsorption and molecular orientation of Dy@C82 isomer I on Au(111) has been investi-gated using ultrahigh-vacuum scanning tunneling microscopy at 80 K. At low coverages, the Dy@C82 molecules tend to grow along the step edges of Au(111), forming small clusters and molecular chains. Adsorption of Dy@C82 on the edges is dominated by the fullerene-substrate interaction and presents various molecular orientations. At higher coverages, the Dy@C82 is found to form ordered islands consisting of small domains of equally oriented molecules. The Dy@C82 molecules in the islands prefer the adsorption configurations with the major C2 axis being approximately parallel to the surface of the substrate. Three preferable orientations of the Dy@C82 molecules are found in a two-dimensional hexagonal close packed overlayer. These observations are attributed to the interplay of the fullerene-substrate interaction and dipole-dipole interaction between the metallofullerenes.
Na+ doped sample Li0.95Na0.05FePO4/C was prepared through solid state method. Structure characterization shows Na+ is successfully introduced into the LiFePO4 matrix. Scanning electron microscopy shows the particle size mainly ranges in 1~3 μm. X-ray diffraction Rietveld refinement demonstrates lattice distortion with an increased cell volume. As one cathode material, it has a discharge capacity of 150 mAh/g at 0.1 C rate. The material exhibits a capacity of 109 and 107 mAh/g at 5 and 7.5 C respectively. When cycled at 1 and 5 C, the material retains 84% (after 1000 cycles) and 86% (after 350 cycles) of the initial discharge capacity respectively indicating excellent structure stability and cycling perfor-mance. Na+doping enhances the electrochemical activity especially the cycle performance effectively.
Catalytic conversion of bio-oil into light olefins was performed by a series of molecular sieve catalysts, including HZSM-5, MCM-41, SAPO-34 and Y-zeolite. Based on the light olefins yield and its carbon selectivity, the production of light olefins decreased in the following order:HZSM-5>SAPO-34>MCM-41>Y-zeolite. The highest olefins yield from bio-oil using HZSM-5 catalyst reached 0.22 kg/kgbio-oil with carbon selectivity of 50.7% and a nearly complete bio-oil conversion. The reaction conditions and catalyst characterization were investigated in detail to reveal the relationship between the catalyst structure and the production of olefins. The comparison between the pyrolysis and catalytic pyrolysis of bio-oil was also performed.
The rheology of the cationic guar (CG) solution was measured and the effects of potassium oleate (KOA) upon the rheological properties of CG solution were studied. The steady shear viscosity measurement has shown that the viscosity of CG solution increased dramatically in the presence of KOA. The viscosity enhancement of KOA upon CG solution can be approximate three orders in magnitude. The gel-like formation of CG solution is observed at the high concentration of KOA. The excess addition of KOA results in the phase separation of CG solution. The oscillatory rheological measurement has shown that the crossover modulus Gc (corresponding to either storage modulus G′ or loss modulus G″ at the frequency wc where G′ equals G″) for CG solution, decreases with the increasing the concentration of KOA in solution. On the other hand, the apparent relaxation time τapp (=1/wc) increases with increasing the concentration of KOA in solution. Our experimental results suggest that for surfactant such as KOA which has a stronger tendency to form micelles in solution, the cooperative hydrophobic interaction of polymer bound to surfactants is less necessary to the formation of aggregates in solution, especially at the high concentration of surfactants. In fact, with the increase of the concentration of KOA, the number of the aggregates which associate polymer together decreases whereas the intensity of these aggregates increases. The effect of temperature upon the aggregation is also significant. With the increase of temperature, the number of the aggregates increases whereas the intensity of these aggregates decreases, probably because the ionization of KOA increases at high temperature.
Nanosized Li4Ti5O12 powders are synthesized by a polymerization-based method using ti-tanium butoxide and lithium nitrate as precursors and furfuryl alcohol as a polymerizable solvent. The prepared samples are characterized by X-ray diffraction, scanning electron mi-croscopy, transmission electron microscopy and Braunauer-Emmett-Teller (BET) analysis. The electrochemical performances of these Li4Ti5O12 powders are also studied. The effect of different surfactants including citric acid, polyvinylpyrrolidone, and cetyltrimethyl am-monium bromide on the structure and properties is also investigated. It is found that pure spinel phase of Li4Ti5O12 is obtained at an annealing temperature of 700 oC or higher. The use of surfactants can improve the powder morphology of nanosized particles with less ag-glomeration. With suitable annealing temperature and the addition of surfactant, Li4Ti5O12 powders with high BET surface area and favorable electrochemical performance can be ob-tained.
A series of poly(acrylic acid) macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer (RAFT) poly-merization and characterized by 1H NMR and gel permeation chromatography. Multirespon-sive core-shell nanogels were prepared by dispersion polymerization of N-isopropylacrylamide in water using these poly(potassium acrylate) macro-RAFT agents as the electrosteric sta-bilizer. The size of the nanogels decreases with the amount of the macro-RAFT agent, indicating that the surface area occupied by per polyelectrolyte group is a critical param-eter for stabilizing the nanogels. The volume phase transition and the zeta potentials of the nanogels in aqueous solutions were studied by dynamic light scattering and zetasizer analyzer, respectively.
The temperature dependence of hydrogen evolution reaction (HER) at a quasi-single crys-talline gold electrode in both 0.1 mol/L HClO4 and 0.1 mol/L KOH solutions was investigated by cyclic voltammetry. HER current displays a clear increase with reaction overpotential (η) and temperature from 278~333 K. In 0.1 mol/L HClO4 the Tafel slopes are found to increases slightly with temperature from 118 mV/dec to 146 mV/dec, while in 0.1 mol/L KOH it is ca. 153±15 mV/dec without clear temperature-dependent trend. The apparent activation energy (Ea) for HER at equilibrium potential is ca. 48 and 34 kJ/mol in 0.1 mol/L HClO4 and 0.1 mol/L KOH, respectively. In acid solution, Ea decreases with increase in η, from Ea=37 kJ/mol (η=0.2 V) to 30 kJ/mol (η=0.35 V). In contrast, in 0.1 mol/L KOH, Ea does not show obvious change with η. The pre-exponential factor (A) in 0.1 mol/L HClO4 is ca. 1 order higher than that in 0.1 mol/L KOH. Toward more negative potential, in 0.1 mol/L HClO4 A changes little with potential, while in 0.1 mol/L KOH it displays a monotonic increase with η. The change trends of the potential-dependent kinetic parameters for HER at Au electrode in 0.1 mol/L HClO4 and that in 0.1 mol/L KOH are discussed.
Nanostructured titanium dioxides were synthesized via various post-treatments of titanate nanofibers obtained from titanium precursors by hydrothermal reactions. The microstruc-tures of TiO2 and supported Ru/TiO2 catalysts were characterized with X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray analysis, and nitrogen adsorption isotherms. The phase structure, particle size, morphology, and specific surface area were de-termined. The supported Ru catalysts were applied for the selective methanation of CO in a hydrogen-rich stream. The results indicated that the Ru catalyst supported on rutile and TiO2-B exhibited higher catalytic performance than the counterpart supported on anatase, which suggested the distinct interaction between Ru nanoparticles and TiO2 resulting from different crystalline phases and morphology.
CuIn(S,Se)2 thin films were prepared by thermal crystallization of co-sputtered Cu-In alloy precursors in S/Se atmosphere. In-depth compositional uniformity is an important prereq-uisite for obtaining device-quality CuIn(S,Se)2 absorber thin films. In order to figure out the influence of heat treatments on in-depth composition uniformity of CuIn(S,Se)2 thin films, two kinds of reaction temperature profiles were investigated. One process is "one step profile", referring to formation of CuIn(S,Se)2 thin films just at elevated temperature (e.g. 500 oC). The other is "two step profile", which allows for slow diffusion of S and Se elements into the alloy precursors at a low temperature before the formation and re-crystallization of CuIn(S,Se)2 thin films at higher temperature (e.g. first 250 oC then 500 oC). X-ray diffrac-tion studies reveal that there is a discrepancy in the shape of (112) peak. Samples annealed with "one step profile" have splits on (112) peaks, while samples annealed with "two step profile" have relatively symmetrical (112) peaks. Grazing incident X-ray diffraction and en-ergy dispersive spectrum measurements of samples successively etched in bromine methanol show that CuIn(S,Se)2 thin films have better in-depth composition uniformity after "twostep profile" annealing. The reaction mechanism during the two thermal processing was also investigated by X-ray diffraction and Raman spectra.
Monodisperse Ag nanoparticles with diameters of about 3.4 nm were synthesized by a facile ultrasonic synthetic route at room temperature with the reduction of borane-tert-butylamine in the presence of oleylamine (OAm) and oleic acid (OA). The reaction parameters of time, the molar ratios of OAm to OA were studied, and it was found that these parameters played important roles in the morphology and size of the products. Meanwhile, surface enhanced Raman spectrum (SERS) property suggested the Ag nanoparticles exhibited high SERS effect on the model molecule Rhodamine 6G. And also, two-photon fluorescence images showed that the silver nanoparticles had high performances in fluorescence enhancement.
Letter
Using density functional theory, we studied band structure, density of states, optical proper-ties and Mulliken population of the pure and SiN doped BaMgAl10O17:Eu2+(BAM:Eu2+) phosphors. Calculation results showed that the bands of BAM:Eu2+ were of low band en-ergy dispersion, indicating large joint density of states, hence high performance of optical absorption and luminescence. BAM:Eu2+ showed stronger absorption intensity while Eu2+ occupied the BR sites instead of the mO sites. The concentration of Eu2+ at BR sites increased while that at mO sites decreased after Si-N doping. The influence of the vari-ation of Eu2+ distribution on the spectra was stronger than the influence of the decrease of Eu2+ PDOS when SiN concentration was lower than 0.25, therefore the absorption andluminescence intensity of BAM:Eu2+ were enhanced. Mulliken population of Si-N bond was higher than Al-O bond, while that of Eu-N bond was higher than Eu-O bond as well, indicating that Si-N bonds and Eu-N bonds possessed higher covalence than Al-O bonds and Eu-N bonds respectively. The existence of Si-N bonds and Eu-N bonds enhanced the local covalence of Eu2+, hence the optical stability of BAM:Eu2+.
Molecular dynamics (MD) simulations are performed to study the structure and adsorption of ethanol/water mixture within carbon nanotubes (CNTs). Inside the (6,6) and (10,10) CNTs, there are always almost full of ethanol molecules and hardly water molecules. Inside wider CNTs, there are some water molecules, while the ethanol mass fractions inside the CNTs are still much higher than the corresponding bulk values. A series of structural analysis for the molecules inside and outside the CNTs are performed, including the distributions of radial, axial, angular density, orientation, and the number of hydrogen bonds. The angular density distribution of the molecules in the first solvation shell outside the CNTs indicates that the methyl groups of ethanol molecules have the strongest interaction with the carbon wall, and are pinned to the centers of the hexagons of the CNTs. Based on the understanding of the microscopic mechanism of these phenomena, we propose that the CNTs prefer to contain ethanol rather than methanol.
We report a simple and green approach to synthesize reduced graphene oxide (RGO) nanosheets at room temperature based on Zn reduction of exfoliated GO. The evolution of GO to RGO has been characterized by X-ray diffraction, UV-Vis absorption spectroscopy and Raman spectroscopy. The results of X-ray photoelectron spectroscopy reveal that the atomic ratio of carbon to oxygen in the RGO can be tuned from 1.67 to 13.7 through controlling the reduction time. Moreover, the conductivity of the RGO is measured to be 26.9±2.2 kS/m, much larger than those previously obtained by chemical reduction through other reducing agents. More importantly, the resistance of the RGO film with 20 nm thick-ness can be as low as 2 kΩ/square, while a high transparency over 70% within a broad spectral range from 0.45 μm to 1.50 μm can be retained. The proposed method is low-cost, eco-friendly and highly-effcient, the as-prepared thinner RGO films are useful in a variety of potential application fields such as optoelectronics, photovoltaics and electrochemistry by serving as an ultralight, flexible and transparent electrode material.
Article
In order to determine the structures of Si(111)-√7×√3-In surfaces and to understand their electronic properties, we construct six models of both hexagonal and rectangular types and perform first-principles calculations. Their scanning tunneling microscopic images and work functions are simulated and compared with experimental results. In this way, the hex-H3' and rect-T1 models are identified as the experimental configurations for the hexagonal and rectangular types, respectively. The structural evolution mechanism of the In/Si(111) surface with indium coverage around 1.0 monolayer is discussed. The 4×1 and √7×√3 phases are suggested to have two different types of evolution mechanisms, consistent with experimental results.
The permselectivity of H2/O2、H2/N2、H2/CO, and H2/CH4 mixtures passing a graphdiyne membrane is studied by molecular dynamics simulations. At pressure range of 0.047~4.5 GPa, H2 can pass the graphdiyen membrane quickly, while all the O2, N2, CO, and CH4 molecules are blocked. At pressure of 47 kPa, the hydrogen flow is 7 mol/m2s. With increase of pressure, the hydrogen flow goes up, and reaches maximum of 6×105 mol/m2s at 1.5 GPa. Compared to other known membranes, graphdiyne can be used for means of hydrogen purification with the best balance of high selectivity and high permeance.