2012 Vol. 25, No. 5

Editorial
A surface photocatalysis-TPD apparatus devoted to studying kinetics and mechanism of pho-tocatalytic processes with various signal crystal surfaces has been constructed. Extremely high vacuum ( 0.2 nPa) in the ionization region is obtained by using multiple ultrahigh vacuum pumps. Compared with similar instruments built previously by others, the H2, CH4 background in the ionization region can be reduced by about two orders of magnitude, and other residual gases in the ionization region can be reduced by about an order of magnitude. Therefore, the signal-to-noise ratio for the temperature programmed desorption (TPD) and time of flight (TOF) spectra is substantially enhanced, making experimental studies of pho-tocatalytic processes on surfaces much easier. In this work, we describe the new apparatus in detail and present some preliminary studies on the photo-induced oxygen vacancy defects on TiO2(110) at 266 nm by using the TPD and TOF methods. Preliminary results suggest that the apparatus is a powerful tool for studying kinetics and mechanism of photochemical processes.
The CS radical was generated by discharging the mixture gas of CS2 and Helium. The Doppler limited spectra of CS were recorded in the region of 12350~12950 cm-1 using optical heterodyne concentration modulation absorption spectroscopy. Three hundred and twenty-six lines were recorded and assigned to the d3△-a3П(8,1) band, in which eighty-three transitions were first observed. A set of improved molecular constants for the d3△(v=8) and a3П(8,1)(v=1) levels were determined by a non-linear least-squares fitting of all the lines to the effective Hamiltonian.
Raman spectra of xLa2O3-(1-x)的TeO2(x=0、0.05、0.10、0.15、0.20和0.25) lanthanum tellurite glasses were measured and analyzed over the entire glass-forming region in an effort to quantitatively follow the structural changes caused by lanthanum oxide variation. For the first time, systematic intensity measurements have been performed to elucidate the composition induced structural changes in the high-frequency stretching vibration region and a possible mechanism was proposed. The network structure of the glasses is formed by mixing TeO4 trigonal bipyramid and TeO3 trigonal pyramid units. The change of the lanthanum oxide content results in conversion of the TeO4 units to TeO3 units with a varying number of non-bridging oxygen atoms. Analysis of the Raman band contours in terms of vibrations due to different oxygen bridged trigonal bipyramid and trigonal pyramid tellurite structural units, allowed to calculate the relative amounts of the species involved in the structural changes with composition. The fraction of the terminal oxygen atoms has been estimated from the Raman intensities with the aid of a structural model concerning the structure of tellurite network systems. The simulation of the experimental density of lanthanum tellurite glasses with modifier content up to 25% revealed that the short range order building units assumed here are sufficient to account for the overall structure in these glasses.
Normal vibrations of ethylbenzene in the first excited state have been studied using resonant two-photon ionization spectroscopy. The band origin of ethylbenzene of S1←S0 transition appeared at 37586 cm-1. A vibrational spectrum of 2000 cm-1 above the band origin in the first excited state has been obtained. Several chain torsions and normal vibrations are obtained in the spectrum. The energies of the first excited state are calculated by the time-dependent density function theory and configuration interaction singles (CIS) methods with various basis sets. The optimized structures and vibrational frequencies of the S0 and S1 states are calculated using Hartree-Fock and CIS methods with 6-311++G(2d,2p) basis set. The calculated geometric structures in the S0 and S1 states are gauche conformations that the symmetric plane of ethyl group is perpendicular to the ring plane. All the observed spectral bands have been successfully assigned with the help of our calculations.
The potential energy curves (PECs) of three low-lying electronic states (X3-, a1△, and A'3△) of SO radical have been studied by ab initio quantum chemical method. The calcula-tions were carried out with the full valence complete active space self-consistent field method followed by the highly accurate valence internally contracted multireference configuration in-teraction (MRCI) approach in combination with correlation-consistent basis sets. Effects of the core-valence correlation and relativistic corrections on the PECs are taken into account. The core-valence correlation correction is carried out with the cc-pCVDZ basis set. The way to consider the relativistic correction is to use the second-order Douglas-Kroll Hamiltonian approximation, and the correction is performed at the level of cc-pV5Z basis set. To obtain more reliable results, the PECs determined by the MRCI calculations are also corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). These PECs are extrapolated to the complete basis set limit by the two-point energy extrapolation scheme. With these PECs, the spectroscopic parameters are determined.
Six low-lying tautomers of 1-methyl-hypoxanthine have been studied at the B3LYP/aug-cc-pVDZ level. Two tautomers N7H and N9H with the comparable energies are far more stable than the others. The vertical ionization energies of the tautomers calculated with ab initio electron propagator theory in the P3/aug-cc-pVDZ approximation are in agreement with the experimental data from photoelectron spectroscopy. According to the calculated relative energies and the comparison between the simulated and the experimental photoelectron spectra, it demonstrates that there are at least two tautomers of 1-methyl-hypoxanthine in the gas-phase experiments.
Based on the full optimized molecular geometrical structures at the DFT-B3LYP/6-311+G** level, there exists intramolecular hydrogen bond interaction for cyclic 2-diazo-4,6-dinitrophenol. The assigned infrared spectrum is obtained and used to compute the thermodynamic properties. The results show that there are four main characteristic regions in the calculated IR spectra of the title compound. The detonation velocities and pressures are also evaluated by using Kamlet-Jacobs equations based on the calculated density and condensed phase heat of formation. Thermal stability and the pyrolysis mechanism of 2-diazo-4,6-dinitrophenol are investigated by calculating the bond dissociation energies at the B3LYP/6-311+G** level.
The prediction of long term failure behaviors and lifetime of aged glass polymers from the short term tests of reduced rupture creep compliance (or strain) is one of difficult problems in polymer science and engineering. A new “universal reduced rupture creep approach” with exact theoretical analysis and computations is proposed in this work. Failure by creep for polymeric material is an important problem to be addressed in the engineering. A universal equation on reduced extensional failure creep compliance for PMMA has been derived. It is successful in relating the reduced extensional failure creep compliance with aging time, temperature, levels of stress, the average growth dimensional number and the parameter in K-W-W function. Based on the universal equation, a method for the prediction of failure behavior, failure strain criterion, failure time of PMMA has been developed which is named as a universal “reduced rupture creep approach”. The results show that the predicted failure strain and failure time of PMMA at di?erent aging times for different levels of stress are all in agreement with those obtained directly from experiments, and the proposed method is reliable and practical. The dependences of reduced extensional failure creep compliance on the conditions of aging time, failure creep stress, the structure of fluidized-domain constituent chains are discussed. The shifting factor, exponent for time-stress superposition at differentlevels of stress and the shifting factor, exponent for time-time aging superposition at different aging time are theoretically defined respectively.
We use density functional theory and time-dependent together with a set of extensive mul-tidimensional visualization techniques to characterize the influence of keto effect on charge distribution at ground state and electronic transitions for neutral and charged hexaphyrin aromaticity with and without keto-defect. It is found that the aromaticity is the key fac-tor to influence the ground state Mulliken charges distribution properties, other than the meso-aryl-substituted effect. But with the enhancement of the keto-defect, the distributionchanges of Mulliken charges on the hexaphyrin groups are larger than those on the pentaflu-orophenyl substituted groups, following with the aromaticity changes from nonaromatic toaromatic. Furthermore, through characterizing by transition density and charge difference density, direct visual evidence for neutral and charged aromaticity with and without keto-defect can be clearly derived, and the ability of charge transfer between units of monoradical (nonaromaticity) and singlet biradical (aromaticity) forms is much stronger than that of neutral forms.
Four acrylamide polymer flocculants, anionic polyacrylamide P(AA-co-AM), cationic poly-acrylamide P(DMB-co-AM), nonionic polyacrylamide P(AM), and hydrophobical polyacry-lamide P(OA-co-AM) have been prepared by copolymerizing with acrylic acid, cationic monomer dimethylethyl (acryloxyethyl) ammonium bromide (DMB) and hydrophobical monomer octadecyl acrylate with acrylamide. The interactions between the flocculants withthe (012) surface of alumina crystal (Al2O3) have been simulated by molecular dynamics method. All the polymers can bind tightly with Al2O3 crystal, the interaction between the O of polymers and Al of the (012) surface of Al2O3 is significantly strong. The order of binding energy is as follows: P(DMB-co-AM)>P(OA-co-AM)>P(AA-co-AM)>P(AM), implying a better flocculation performance of P(DMB-co-AM) than the others. Analy-sis indicates that binding energy is mainly determined by Coulomb interaction. Bonds are found between the O atoms of the polymers and the Al atoms of Al2O3. The poly-mers' structures deform when they combine with Al2O3 crystal, but the deformation en-ergies are low and far less than non-bonding energies. Flocculation experiments in sus-pension medium of 1%Kaolin show a transmittancy of 90.8% for 6 mg/L P(DMB-co-AM) and 73.0% for P(AM). The sequence of flocculation performance of four polymers is P(DMB-co-AM)>P(OA-co-AM)>P(AA-co-AM)>P(AM), which is in excellent agreement with the simulation results of binding energy.
Steady-state absorption and fluorescence spectra, and time-resolved fluorescence spectra of coumarin 343 (C343) were measured in different solvents. The effect of the solvent on the spectral properties and dipole moment of the lowest excited state of C343 were investigated. It was found that the absorption and fluorescence spectra red-shifted slightly and strongly with increasing solvent polarity, respectively, because the charge distribution of the excited state leaded to the increasing difference between the absorption and fluorescence spectra with increasing solvent polarity. The dipole moment of the lowest excited state of C343was determined from solvatochromic measurements and the quantum chemical calculation, and the results obtained from these two methods were fully consistent. Investigations of the time-resolved fluorescence of C343 in different solvents indicated that the fluorescence lifetimes increased nearly linearly with increasing solvent polarity from 3.09 ns in toluene to 4.45 ns in water. This can be ascribed to the intermolecular hydrogen bonding interactions between C343 and hydrogen donating solvents.
The direct hydroxylation of benzene to phenol catalyzed by activated carbon-supported Fe (Fe/AC) in acetonitrile using H2O2 as the oxidant was studied in a continuous flow reactor. Results showed that the continuous operation could obtain high phenol yield of 28.1%, coupled with the turnover frequency of 3 h-1, and high selectivity of 98% under mild condition. The catalyst was characterized by N2 adsorption/desorption, Boehm titration, X-ray photoelectron spectra, and Fourier transform infrared spectroscopy. It was observed that iron may interact with the carboxyl group forming iron-carboxylate like species, which act as the active phase. The apparent activation energy obtained by fitting an Arrhenius model to the experimental data was 13.4 kJ/mol. The reaction order was calculated to be about 1, 0.2 for benzene and 0.7 for H2O2.
To gain insight into the attachment of ≡Si+ (SC) ion (regarded as guest) to the lowest generation, NH2-terminated poly(amidoamine) (PAMAM) dendrimers (regarded as host) in the liquid phase, density functional theory is used to investigate the structures and energetics of the host-guest complex. The effect of solvent on the structures and energetics is also investigated. Various initial configurations of the ion bound to PAMAM are tested, and two stable conformers are found, i.e, types A (≡Si+ is bound to the amine site) and C (≡Si+ is bound to the amide site). Types A and C are the most stable due to the chemical bond formations of Si-No(amine nitrogen atoms) and Si-O, respectively. The IR spectra for the lowest energy conformers are thoroughly analyzed and compared with the available experimental data.
A cobalt-free perovskite-type Ba0.5Sr0.5Al0.1Fe0.9O3-δ (BSAF) is developed and electro-chemically studied as solid oxide fuel cell (SOFC) cathode. The structures, electrical con-ductivity, and electrode polarizations in symmetrical cell based on mixed ion conducting electrolyte were investigated, respectively. The temperature dependence of conductivity of BSAF in air shows a typical semiconductor behavior with positive temperature coefficient up to 450 oC where the conductivity reaches 14.0 S/cm while above this temperature the negative temperature coefficient dominates the total conductivity. Electrochemical charac-terizations show desirable polarization resistance of BSAF cathode in a symmetric cell based on mixed ion conducting electrolyte at 650-700 oC. A single SOFC with BSAF cathode shows OCV of 1.0 V and maximum output of 420 mW/cm2 at 700 oC with humidified hydrogen fuel and static air oxidant.
Mesoporous TiO2 (m-TiO2) nanoparticles were used to prepare the porous film electrodes for dye-sensitized solar cells, and a second metal oxide (MgO, ZnO, Al2O3, or NiO) modifi-cation was carried out by dipping the m-TiO2 electrode into their respective nitrate solution followed by annealing at 500 oC. Experimental results indicated that the above second metal oxide modifications on m-TiO2 electrode are shown in all cases to act as barrier layer for the interfacial charge transfer processes, but film electron transport and interfacial charge recombination characteristics under applied bias voltage were dependent significantly on the existing states and kinds of these second metal oxides. Those changes based on sec-ond metal oxide modifications showed good correlation with the current-voltage analyses of dye-sensitized solar cell, and all modifications were found to increase the open-circuit photo-voltage in various degrees, while the MgO, ZnO, and NiO modifications result in 23%, 13%, and 6% improvement in cell conversion efficiency, respectively. The above observations indi-cate that controlling the charge transport and recombination is very important to improve the photovoltaic performance of TiO2-based solar cell.
Molecular simulation of charged colloidal suspension is performed in NVT canonical ensemble using Monte Carlo method and primitive model. The well-known Derjaguin-Landau-Verwey-Overbeek theory is applied to account for effective interactions between particles. Effect of temperature, valance of micro-ions and the size of colloidal particles on the phase stability of the solution is investigated. The results indicate that the suspension is more stable at higher temperatures. On the other hand, for a more stable suspension to exist, lower micro-ion valance is favorable. For micro-ions of higher charge the number of aggregates and the number of particle in each of aggregate on average is higher. However for the best of our results larger colloidal particle are less stable. Comparing the results with theoretical formula considering the influence of surface curvature shows qualitative consistency.
Organic solar cells with inverted planar heterojunction structure based on subphthalocya-nine and C60 were fabricated using several kinds of materials as cathode buffer layer (CBL), including tris-8-hydroxy-quinolinato aluminum (Alq3), bathophenanthroline (Bphen), bathocuproine, 2,3,8,9,14,15-hexakis-dodecyl-sulfanyl-5,6,11,12,17,18-hexaazatrinaphthylene (HATNA), and an inorganic compound of Cs2CO3. The influence of the lowest unoccupied molecular orbital level and the electron mobility of organic CBL on the solar cells perfor-mance was compared. The results showed that Alq3, Bphen, and HATNA could significantly improve the device performance. The highest efficiency was obtained from device with an-nealed HATNA as CBL and increased for more than 7 times compared with device without CBL. Furthermore, the simulation results with space charge-limited current theory indicated that the Schottky barrier at the organic/electrode interface in inverted OSC structure was reduced for 27% by inserting HATNA CBL.