2013 Vol. 26, No. 4

2013, 26(4): 0-0. doi: 10.1088/1674-0068/26/4/0-0
The mesoscopic structures of β-HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)-based PBXs (polymer bonded explosives) at room temperature were investigated using dissipative particle dynamics method. The parameters and repulsive parameters of dif-ferent polymers and β-HMX, the mesoscopic structures of β-HMX-based polymer-bonded explosives at different temperatures have been studied. The results showed that the compat-ibility between β-HMX and vinylidenedifluoride (VDF), β-HMX and chlorotrifluoroethylene(CTFE), VDF and CTFE increased with increasing temperature. The temperature and mo-lar ratio of the polymers played an important role in wrapped process. And there exists the optimum temperature and molar ratio.
The description and function characterization of a flange-on type low energy electron mi-croscope are given. In this microscope a magnetic beam separator with 10o deflection angle is used in order to facilitate compacting the instrument on a single 10 in. flange. Mean-while some correcting elements in the electron optical system are simplified to reduce the complexities of construction and operation. The sample is set close to ground potential, so that all the electrostatic lenses are easily to float at high voltages. The performance of the microscope in typical low energy electron microscopy, low energy electron diffraction and photoemission electron microscopy modes is demonstrated through several experiments. A lateral resolution of 51 nm is estimated for low energy electron microscopy imaging. With femtosecond laser as light source, the consequent nonlinear photoemission makes this micro-scope also suitable for the observation of optical near field phenomena and a lateral resolution of 110 nm is obtained.
The even-parity autoionizing resonance series 5p5np'[3/2]1, [1/2]1, and 5p5nf'[5/2]3 of xenon have been investigated, excited from the two metastable states 5p56s[3/2]2 and 5p56s'[1/2]0 in the photon energy range of 28000-42000 cm-1 with experimental bandwidth of ~0.1 cm-1. The excitation spectra of the even-parity autoionizing resonance series show typical asymmetric line shapes. New level energies, quantum defects, line profile indices and resonance widths, resonance lifetimes and reduced widths of the autoionizing resonances are derived by a Fano-type line-shape analysis. The line profile index and the resonance width are shown to be approximately proportional to the effective principal quantum number. The line separation of the 5p5np' autoionizing resonances is discussed.
The conformers of allyl alcohol and allyl mercaptan were studied with B3LYP/aug-cc-pVTZ method. Their relative energies were calculated at MP3, MP4(SDQ), and CCSD(T) levels. The most stable conformers for these two molecules are Gauche-gauche' (Gg'). The theo-retical photoelectron spectra simulated with the calculated ionization energies demonstrate that there are at least four conformers in allyl alcohol and four conformers in allyl mercaptan in the gas-phase experiments. The Dyson orbitals of the highest occupied molecular orbital (HOMO) and the next HOMO (HOMO-1) of allyl mercaptan Gg' conformer show strongly mixing nS and πC=C characteristics, which may be due to the resonance and inductive effects between πC=C and nS in HOMO-1 and HOMO.
The photo-physical characteristics of semiconductor polymer are systematically stud-ied through comparing poly (9,9-dioctylfluorene) (PFO) and poly (9,9-dioctylfluorene-co-benzothiadiazole) (F8BT). The quantum chemical calculation shows that the introduction of benzothiadiazole unit facilitates the intrachain charge transfer (ICT) and modulates the electronic transition mechanism of polymer. The transient absorption measurement exhibits that intrachain exciton relaxation is dominant in the decay of excited PFO in a monodis-perse system and intrachain exciton interaction could appear at high excitation intensity. In F8BT solution, the ICT state exists and participates in the relaxation of excited state. The relaxation processes of PFO and F8BT in the condensed phase both accelerate and show obvious exciton-exciton annihilation behavior at high excitation intensity. At the same excitation intensity, the mean lifetime of F8BT is longer than that of PFO, which may be assigned to the excellent delocalization of charge.
Resonant electron injection and first-principles calculations are utilized to study single-adsorbed selenium (Se) atom on a Si(111)-7×7 surface. Theoretical calculations indicate that a negative dipole of 0.61 eV forms toward the adsorbed Se atom due to electron trans-fer from the associated Si atoms. The formation of surface dipole modifies the effective tunneling barrier height and causes a shift in the energy of the resonant state formed in the vacuum gap between the tip and the sample surface. The experimental data imply that an outward negative surface dipole of 0.61 eV causes a resonant electron injection bias shift to high voltage of about 0.45 V.
The infrared absorption and Raman scattering spectra were measured for the metallotriph-enylcorroles (MTPCs, M=Cu, Co, Ni, Mn). The ground-state structures and vibrational spectra of MTPCs have been calculated with the density functional theory. The observedRaman and IR bands have been assigned based on the calculation results. Due to the symmetry lowering, the vibrational spectra of MTPCs are much more complex than metal-loporphyrins, and several skeletal modes are found strongly coupled to the phenyl vibrations.The relationship between the Raman/IR frequencies and the structures of TPC ring is in-vestigated. It is found that the vibrations involving the CIαCIα stretch and CαCmstretch are sensitive to the size of corrole core. In particular, the frequency of υ5, which is assigned to CIαCIα stretch in coupling with the CαCm symmetric stretch, increases linearly with the decrease of the corrole core-sizes and may be used as a mark band to evaluate the structural change of the metallocorroles.
We present theoretical investigations on structure-property correlations in fluorenone (FLO) and benzothiadiazole (BT) substituted oligofluorenes (OFLs) derived mainly from the chain morphology, thermal vibration and conjugated extent. Both the vertical absorptions and the vibrationally-resolved absorption and fluorescence spectra have been calculated by the com-bination of ab initio and time-dependent density functional theory. By properly taking into account of the anharmonic torsion potentials in the OFLs, we have reasonably reproduced the experimentally observed spectroscopic features. Both FLO and BT on-chain chemical defects acting as charge-trapping sites for singlet excitations, are responsible for long wave absorption and emission species, and thus alter the blue light-emitting properties of OFLs. As temperature decreases, the electronic spectral lineshapes of FLO-substituted oligomers become more structured. The lineshapes of BT-substituted oligomers are always smooth and featureless because of less low collective modes resonance. A more gentle excited poten-tial energy surface of BT-mixed molecules can enhance electronic delocalization and achievebigger red shifts.
Pd-catalyzed oxidative C-H/C-H coupling reaction is an emerging type of C-H acti-vation reaction, which attracts great interests because both reaction partners do not re-quire pre-functionalization. In the present study, we employed DFT methods to investigatethe mechanism of Pd(OAc)2-catalyzed oxidative C-H/C-H coupling of pentafluoroben-zene with benzene. Four possible pathways were examined in the C-H activation part: path A benzene-pentafluorobenzene mechanism (C-H activation of benzene occurs before the C-H activation of pentafluorobenzene), path B pentafluorobenzene-benzene mechanism (C-H activation of benzene occurs after the C-H activation of pentafluorobenzene), path C benzene-pentafluorophenylsilver mechanism (C-H activation of benzene and subsequenttransmetalation with pentafluorophenyl silver complex), path D pentafluorophenylsilver-benzene mechanism (transmetalation with pentafluorophenyl silver complex and subsequent C-H activation of benzene). Based on the calculations, the sequences of two C-H activation steps are found to be different in the oxidative couplings of same substrates (i.e. pentaflu-orobenzene and benzene) in different catalytic systems, where the additive Ag salts played a determinant role. In the absence of Ag salts, the energetically favored pathway is path B (i.e. the C-H activation of pentafluorobenzene takes place before the C-H cleavage of benzene). In contrast, with the aid of Ag salts, the coordination of pentafluorophenylsilver to Pd center could occur easily with a subsequent C-H activation of benzene in the second step, and the second step significantly raises the whole reaction barrier. Alternatively, in thepresence of Ag salts, the kinetically preferred mechanism is path C (i.e. the C-H activation of benzene takes place in the first step followed by transmetalation with pentafluorophenyl-silver complex), which is similar to path A. The calculations are consistent with the H/D exchange experiment and kinetic isotope effects. Thus the present study not only offers a deeper understanding of oxidative C-H/C-H coupling reaction, but also provides helpful insights to further development of more efficient and selective oxidative C-H/C-H coupling reactions.
Various manganese oxide nanorods with similar one-dimensional morphology were prepared by calcination of MnOOH nanorods under different gas atmosphere and at different temper-atures, which were synthesized by a hydrothermal route. The morphology and structure of MnOx catalysts were characterized by a series of techniques including X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and tempera-ture programmed reduction (TPR). The catalytic activities of the prepared MnOx nanorods were tested in the liquid phase aerobic oxidation of benzyl alcohol, which follow a sequence as MnO2>Mn2O3≈Mn3O4>MnOOH with benzaldehyde being the main product. On the basis of H2-TPR results, the superior activity of MnO2 is ascribed to its lower reduction temperature and therefore high oxygen mobility and excellent redox ability. Moreover, a good recycling ability was observed over MnO2 catalysts by simply thermal treatment in air.
Electrical properties and magnetoresistance have been studied in two series of xAg-La0.67(Ca0.65Ba0.35)0.33MnO3 and xPd-La0.67(Ca0.65Ba0.35)0.33MnO3 (abbreviated by xAg-LCBMO and xPd-LCBMO) composites. Both Pd and Ag addition induce a decrease in resistivity and an increase in temperature at which the resistivity reaches its maximum. This is mainly due to the improvement of grain boundaries caused by the segregation of good conductive metal grains on the grain boundaries/surfaces. In addition, both Pd and Ag addition induce a large enhancement of room temperature magnetoresistance (RTMR). Note that 27% molar ratio of Ag addition induces a large RTMR of about 70%, about ten times larger than pure LCBMO, whereas 27% molar ratio Pd addition brings a much larger RTMR of about 170%. The large enhancements of MR can be attributed to the decrease in resistivity of the samples caused by the good conductive metal. On the other hand, the polarization of Pd atoms near the Mn ions on the grain surfaces/boundaries plays a very im-portant role in the increase in MR, which induces a large number of spin clusters in Pd-added samples.
N-Methyl-N-propylpiperidiniumbis(trifluoromethanesulfonyl)imide (PP13TFSI), bis(triflu-oromethanesulfonyl)imide lithium salt (LiTFSI), and poly(vinylidene difluoride-co-hexafluoropropylene) (P(VdF-HFP)) were mixed and made into ionic liquid gel polymerelectrolytes (ILGPEs) by solution casting. The morphology of ILGPEs was observed by scanning electron microscopy. It was found that the ILGPE had a loosened structure with liquid phase uniformly distributed. The ionic conductivity, lithium ion transference num-ber and electrochemical window were measured by electrochemical impedance spectroscopy, chronoamperometric and linear sweep voltammetry. The ionic conductivity and lithium ion transference number of this ILGPE reached 0.79 mS/cm and 0.71 at room temperature, and the electrochemical window was 0 to 5.1 V vs. Li+/Li. Battery tests indicated that the ILGPE is stable when being operated in Li/LiFePO4 batteries. The discharge capacity maintained at about 135, 117, and 100 mAh/g at 30, 75, and 150 mA/g rates, respectively. The capacity retentions were almost 100% after 100 cycles without little capacity fading.
Polyurethane/polyhedral oligomeric sisesquioxane (PU/POSS) nanocomposites were syn-thesized via polymerization utilizing the compatibility between POSS nanoparticles and 4,4'-diphenyl methylene diisocyanate. Scanning electron microscope images and Fouriertransform infrared spectra revealed that POSS nanoparticles were dispersed in PU matrix.Thermal gravimetric analysis was employed to investigate the thermal decomposition be-havior of PU/POSS nanocomposites at elevated temperatures. Then fire performance wasevaluated by limiting oxygen index, underwriters laboratories 94 testing and char residue morphology. These results showed that the addition of POSS promoted the formation of char residues which were covered on the surface of polymer composites, leading to the im-provement of thermal stability and flame retardancy.
Flower-like NaY(MoO4)2 particles were synthesized through a microwave-assisted hydrother-mal process followed by a subsequent calcination process. The products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scanning electron mi-croscopy. The possible formation mechanism of the flower-like NaY(MoO4)2 precursor was proposed. The NaY(MoO4)2:Eu3+ phosphors were also prepared and their luminescence properties showed the NaY(MoO4)2:Eu3+ materials with the emission peak at 612 nm had potential application as a red phosphor for white light-emitting diodes. Furthermore, the microwave-assisted hydrothermal process followed by a subsequent calcination process could be extended to prepare the other lanthanide molybdates with the flower-like morphology.
Zn0.95-xAlxMn0.05O (x=0, 0.03, 0.05, and 0.07) dilute magnetic semiconductor materials have been synthesized by sol-gel auto-combustion technique. The effect of Al doping on the structural, electrical, and magnetic properties has been investigated. X-ray diffraction studies demonstrate the existence of single phase characteristic hexagonal wurtzite type crystal structure, similar to the host ZnO, in all the synthesized compositions. Although, the microscopic images revealed that the grains were clustered, yet some individual grains could be seen to have hexagonal texture. Electrical resistivity was observed to decrease with the rise of temperature up to 450 oC, depicting the characteristic semiconductor behavior. Room temperature ferromagnetic behavior was observed in all the compositions. The value of saturation magnetization increased with the increase of Al concentration in ZnMnO system referred to the gradual enhancement of free carriers.
With on-line coupled thermo-gravimetric analyzer-Fourier transform infrared spectrometer technique, the thermal decomposition of lithium hexafluorophosphate (LiPF6) and its gas evolution at inert environment (H2O<10 ppm) were studied under both non-isothermal and isothermal conditions. The results showed that the LiPF6 decomposition is a single-stage reaction with LiF as final residue and PF5 as gas product. In addition, its decomposi-tion kinetics was determined as 2D phase boundary movement (cylindrical symmetry) under both non-isothermal and isothermal conditions. Furthermore, the activation energy of LiPF6 decomposition was calculated as 104 and 92 kJ/mol for non-isothermal and isothermal con-ditions, respectively.
Formic acid (HCOOH) decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate (HCOOb) is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH-containing solution at constant potential (E=0.4 V vs. RHE), we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.
Production of benzene, toluene and xylenes (BTX) from bio-oil can provide basic feedstocks for the petrochemical industry. Catalytic conversion of bio-oil into BTX was performed by using different pore characteristics zeolites (HZSM-5, HY-zeolite, and MCM-41). Based on the yield and selectivity of BTX, the production of aromatics decreases in the following order: HZSM-5>MCM-41>HY-zeolite. The highest BTX yield from bio-oil using HZSM-5 reached 33.1% with aromatics selectivity of 86.4%. The reaction conditions and catalystcharacterization were investigated in detail to make clear the optimal operating parameters and the relation between the catalyst structure and the production of BTX.
ondary organic aerosol (SOA) formation from OH-initiated photo-oxidation of isoprene in the presence of organic seed aerosol. The dependence of the size distributions of SOA on both the level of pre-existing particles generated in situ from the photo-oxidation of trace hydrocarbons of indoor atmosphere and the concentration of precursor, has been investi-gated. It was shown that in the presence of high-level seed aerosol and low-level isoprene (typical urban atmospheric conditions), particle growth due to condensation of secondary organic products on pre-existing particles dominated; while in the presence of low-level seed aerosol and comparatively high-level isoprene (typical atmospheric conditions in rural re-gion), bimodal structures appeared in the size distributions of SOA, which corresponded to new particle formation resulting from homogeneous nucleation and particle growth due to condensation of secondary organic products on the per-existing particles respectively. The effects of concentrations of organic seed particles on SOA were also investigated. The particle size distributions evolutions as well as the corresponding formation rates of new particles indifferent conditions were also estimated.