2015 Vol. 28, No. 3

2015, 28(3): 0-0.
Combining Raman spectroscopy with density functional theory, the populations of the trans- and gauche- ethanol conformers are investigated in carbon tetrachloride (CCl4) and carbon disulfide (CS2). The spectral contributions of two ethanol conformers are identified in OH stretching region. The energy difference between both conformers is estimated with the aid of the calculated Raman cross sections. It can be seen that the trans- ethanol is more stable in CCl4 and CS2 solutions. The spectra are also obtained at different temperatures, and it is found the van't Hoff analysis is invalid in these solutions. By taking accounts of the Boltzmann distribution and theoretical Raman cross section, the energy difference is found to be increased with temperature, which shows the weak intermolecular interactions can enhance the population of trans- ethanol.
We measure the dispersed spectrum of the A2Π~X2Σ+ system of MgH using laser abla-tion/laser induced Fluorescence method and obtain the Frank-Condon factors and related transition frequencies of the A2Π(v′=0)-X2Σ+(v〞=0,1) system by analyzing the experimen-tal spectrum. Also, we calculate the Franck-Condon factors and transition frequencies of the A2Π~X2Σ+ system of MgH. A comparison of our theoretical calculation and experimental results with other reported theoretical results was carried out as well.
Optical limiting (OL) properties and two-photon absorption (TPA) of a series of covalently linked graphene oxide-porphyrin composite materials have been investigated by numerically solving the rate equations and field intensity equation with an iterative predictor-corrector finite-difference time-domain technique in nanosecond time domain. Our results show that graphene oxide-porphyrin composites exhibit enhanced OL behavior and possess larger TPA cross section compared with individual porphyrins. Interestingly, unlike the previous result that porphyrin with heavier central metal shows better nonlinear abilities than that with-out metal substitute, graphene oxide-metal free porphyrin composite has stronger nonlinear absorption properties compared with graphene oxide-metal porphyrin composite. The com-putational results are in reasonable agreement with the experimental ones. Special attention has been paid to the influence of thickness of the medium and pulse width on TPA cross sections, which presents that larger TPA cross sections are obtained as the medium is thicker or the pulse duration is wider.
The structural and thermodynamic properties of Zr2AlC at high pressure and high temperature are investigated by first principles density functional theory method. The calculated lattice parameters of Zr2AlC are in good agreement with the available theoretical data. The pressure dependences of the elastic constants, bulk modulus, shear modulus, Young's modulus, and Vickers hardness of Zr2AlC are successfully obtained. The elastic anisotropy is examined through the computation of the direction dependence of Young's modulus. By using the quasiharmonic Debye model, the thermodynamic properties including the Debye temperature, heat capacity, volume thermal expansion coefficient, and Grüneisen parameter at high pressure and temperature are predicted for the first time.
The free-radical-based selective desulfurization of cysteine residue is an e cient protocol to achieve ligations at alanine sites in the synthesis of polypeptide and proteins. In this work, the mechanism of desulfurization process has been studied using the density functional theory methods. According to the calculation results, the desulfurization of the thiol group occurs via a three-steps mechanism: the abstraction of hydrogen atom on the thiol group with the radical initiator VA-044 (2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride), the removal of S atom under the reductant TCEP (tris(2-carboxyethyl)phosphine), and theformation of RH molecule (with the regeneration of RS radical). The second step (desulfurization step) is the rate-determining step, and the adduct t-BuSH facilitates the desulfurization of cysteine via bene ting the formation of the precursor of the desulfurization step.
A Michael addition is usually taken as a base-catalysed reaction. However, our synthesized 2-(quinolin-2-ylmethylene) malonic acid (QMA) as a Michael-type thiol fluorescent probe is acid-active in its sensing reaction. In this work, based on theoretic calculation and experi-mental study on 7-hydroxy-2-(quinolin-2-ylmethylene) malonic acid, we demonstrated that QMA as a Michael acceptor is acid-activatable, i.e., it works only in solutions at pH<7, and the lower the pH of solutions is, the higher reactivity QMA has. In alkaline solution, the malonate QMA[-2H+]2- cannot react with both RS- and RSH. In contrast, 2-(quinolin-2-ylmethylene) malonic ester (QME), the ester of QMA, reveal a contrary pH effect on its sensing reaction, that is, it can sense thiols in alkaline solutions but not in acidic solutions, like a normal base-catalysed Michael addition. The values of activation enthalpies from theoretic calculation support the above sensing behavior of two probes under different pH conditions. In acidic solutions, the protonated QMA is more highly reactive towards elec-trophilic attack over its other ionized states in neutral and alkaline solutions, and so can react with lowly reactive RSH. In contrast, there is a big energy barrier in the interaction of QME with RSH (acidic solutions), and the reaction of QME with the highly reactive nucle-ophile RS- is a low activation energy process (in alkaline solutions). Theoretic calculation reveals that the sensing reaction of QMA undergoes a 1,4-addition process with neutral thiols (RSH), and a 1,2-addition pathway for the sensing reaction of QME with RS-. Therefore, the sensing reaction of QMA is an acid-catalysed Michael addition via a 1,4-addition, and a normal base-catalysed Michael addition via a 1,2-addition.
Phase equilibria of hydrogen bonding (HB) fluid confined in a slit pore with broken symmetry were investigated by the density functional theory incorporated with modified fundamental measure theory, where the symmetry breaking originated from the distinct interactions between fluid molecules and two walls of the slit pore. In terms of adsorption-desorption isotherms and the corresponding grand potentials, phase diagrams of HB fluid under various conditions are presented. Furthermore, through phase coexistences of laying transition and capillary condensation, the effects of HB interaction, pore width, fluid-pore interaction and the broken symmetry on the phase equilibrium properties are addressed. It is shown that these factors can give rise to apparent influences on the phase equilibria of confined HB fluid because of the competition between intermolecular interaction and fluid-pore interaction. Interestingly, a significant influence of broken symmetry of the slit pore is found, and thus the symmetry breaking can provide a new way to regulate the phase behavior of various confined fluids.
The dynamics of quantum entanglement described by the von Neumann entropy is studied for the localized states of Fermi-resonance coupling vibrations in molecule CS2, where the interacting energy between the stretching and the bending modes is considered to establish a connection between entanglement and energy. It is shown that entanglement reveals dominant anti-correlation with the interacting energy for the stretch-localized state, while that exhibits dominantly positive correlation for the bend-localized state. The entanglement and the energy for the dislocalized states are discussed as well. Those are useful for molecular quantum computing and quantum information in high dimensional states.
Internal reformation of low steam methane fuel is important for the high e ciency and low cost operation of solid oxide fuel cell. Understanding and overcoming carbon deposition is crucial for the technology development. Here a multi-physics model is established for the relevant experimental cells. Balance of electrochemical potentials for the electrochemical reactions, generic rate expression for the methane steam reforming, dusty gas model in a form of Fick's model for anode gas transport are used in the model. Excellent agreement between the theoretical and experimental current-voltage relations is obtained, demonstrating the validity of the proposed theoretical model. The steam reaction order in low steam methane reforming reaction is found to be 1. Detailed information about the distributions of physical quantities is obtained by the numerical simulation. Carbon deposition is analyzed in detail and the mechanism for the coking inhibition by operating current is illustrated clearly. Two expressions of carbon activity are analyzed and found to be correct qualitatively, but not quantitatively. The role of anode diffusion layer on reducing the current threshold for carbon removal is also explained. It is noted that the current threshold reduction may be explained quantitatively with the carbon activity models that are only qualitatively correct.
Trans-sobrerol (Sob) and 8-p-menthen-1,2-diol (Limo-diol) are the primary products in the atmospheric oxidation of α-pinene and limonene, respectively. Because of their low volatility, they associate more likely to the liquid particles in the atmosphere, where they are subject to the aqueous phase oxidation by the atmospheric oxidants. In this work, through experimental and theoretical study, we first provide the rate constants of Sob and Limo-diol reacting with hydroxyl radical (·OH) in aqueous solution at room temperature of 304±3 K and 1 atm pressure, which are (3.05±0.5)×109 and (4.57±0.2)×109 L/(mol·s), respectively. Quantum chemistry calculations have also been employed to demonstrate the solvent effect on the rate constants in aqueous phase and the calculated results agree well with the measurements. Some reaction products have been identified based on liquid chromatography combined with mass spectroscopy and theoretical calculations.
The electrochemical stability of LiFePO4 in a Li+-containing aqueous electrolyte solution is critically dependent on the pH value of the aqueous solution. It shows a considerable decay in capacity of LiFePO4 upon cycling when the pH value is increased to 11. The mechanism responsible for the capacity fading is extensively investigated by means of cyclic voltammogram, ac impedance, charge/discharge, ex situ X-ray diffraction, and chemical analysis. LiFePO4 is relatively electrochemically stable in LiNO3 aqueous solution with pH=7. But the electrochemical performance of LiFePO4 in aqueous electrolyte is inferior to that in organic electrolyte. It is attributed to the loss of Li and the Fe, P dissolution during prolonged charge-discharge in aqueous medium. A precipitate is formed on the surface of LiFePO4 electrodes. It results in the change of crystalline structure, a large electrode polarization, and capacity fading.
Ni/YSZ fuel electrodes can only operate under strongly reducing conditions for steam electrolysis in an oxide-ion-conducting solid oxide electrolyzer (SOE). In atmosphere with a low content of H2 or without H2, cathodes based on redox-reversible Nb2TiO7 provide a promising alternative. The reversible changes between oxidized Nb2TiO7 and reduced Nb1.33Ti0.67O4 samples are systematically investigated after redox-cycling tests. The conductivities of Nb2TiO7 and reduced Nb1.33Ti0.67O4 are studied as a function of temperature and oxygen partial pressure and correlated with the electrochemical properties of the composite electrodes in a symmetric cell and SOE at 830 oC. Steam electrolysis is then performed using an oxide-ion-conducting SOE based on a Nb1.33Ti0.67O4 composite fuel electrode at 830 oC. The current-voltage and impedance spectroscopy tests demonstrate that the reduction and activation of the fuel electrode is the main process at low voltage; however, the steam electrolysis dominates the entire process at high voltages. The Faradic efficiencies of steam electrolysis reach 98.9% when 3%H2O/Ar/4%H2 is introduced to the fuel electrode and 89% for that with introduction of 3%H2O/Ar.
The V2O3-C dual-layer coated LiFePO4 cathode materials with excellent rate capability and cycling stability were prepared by carbothermic reduction of V2O5. X-ray powder diffraction, elemental analyzer, high resolution transmission electron microscopy and Raman spectra revealed that the V2O3 phase co-existed with carbon in the coating layer of LiFePO4 particles and the carbon content reduced without graphitization degree changing after the carbothermic reduction of V2O5. The electrochemical measurement results indicated that small amounts of V2O3 improved rate capability and cycling stability at elevated temperature of LiFePO4/C cathode materials. The V2O3-C dual-layer coated LiFePO4 composite with 1wt% vanadium oxide delivered an initial specific capacity of 167 mAh/g at 0.2 C and 129 mAh/g at 5 C as well as excellent cycling stability. Even at elevated temperature of 55 oC, the specific capacity of 151 mAh/g was achieved at 1 C without capacity fading after 100 cycles.
A series of Ni based catalysts with different supports and basic additives were prepared by sequential impregnation method. The catalysts were characterized by XRD, BET, H2-TPR and CO2-TPD techniques. It was found that the introduction of basic additives enhanced the basicities of catalyats and promoted the dispersities of Ni particles by strong interaction between Ni2+ and basic additives. Among the Ni based catalysts, 10%Ni/10%La2O3/ZrO2 showed the superior performance in sorbitol hydrogenolysis. The synergistic effect of Ni and La2O3 was proven to play an essential role in selective synthesis of EG and 1,2-PG. In the optimal reaction condition, the catalyst presented 100% sorbitol conversion and over 48% glycols (EG and 1,2-PG) yield. The kinetics study of polyols (sorbitol, xylitol and glycerol) hydrogenolysis showed that polyols with more hydroxyl number have higher activity and products distribution was final results of kinetic balance, which could give us some inspiration about how to change the products selectivity.
The influence of water vapor on silica membrane with pore size of 4 ? has been investigated in terms of adsorption properties and percolation effect at 50 and 90 oC. Two methods are employed: spectroscopic ellipsometry for water vapor adsorption and gas permeation of binary mixture of helium and H2O. The adsorption behaviors on the silica membrane comply with the first-order Langmuir isotherm. The investigation demonstrates that helium flux through the silica membrane decreases dramatically in presence of H2O molecules. The transport of gas molecules through such small pores is believed not to be continuous any more, whereas it is reasonably assumed that the gas molecules hop from one occupied site to another unoccupied one under the potential gradient. When the coverage of H2O molecules on the silica surface increases, the dramatic decrease of helium flux could be related to percolation effect, where the adsorbed H2O molecules on the silica surface block the hopping of helium molecules.
The Ho3+/Yb3+ co-doped α-NaYF4 single crystal was grown successfully for the first time by a modified Bridgman method in which KF was used as assisting flux and a large temperature gradient (70-90 oC/cm) of solid-liquid interface was adopted. Upconversion emissions at green ~544 nm, red ~657 and ~751 nm were obtained under 980 nm laser diode excitation. The intensity at ~544 nm was much stronger than those of ~657 and ~751 nm. The mechanisms of the upconversion emissions were investigated by studying the relationship between the upconversion intensity and pump power. The optimized Yb3+ concentration was about 8.08 mol% when Ho3+ concentration was hold at about 1.0 mol%. The results showed that Ho3+/Yb3++ doped α-NaYF4 single crystal was a possible candidate upconversion material for the green solid-state laser.
The biorefinery process for sugarcane bagasse saccharification generally requires significant accessibility of cellulose. We reported a novel method of cascade cellulase enzymatic hydrolysis coupling with ultrafine grinding pretreatment for sugarcane bagasse saccharification. Three enzymatic hydrolysis modes including single cellulase enzymatic hydrolysis, mixed cellulase enzymatic hydrolysis, and cascade cellulase enzymatic hydrolysis were compared. The changes on the functional group and surface morphology of bagasse during cascade cellulase enzymatic hydrolysis were also examined by FT-IR and SEM respectively. The results showed that cascade enzymatic hydrolysis was the most efficient way to enhance the sugarcane bagasse sacchari cation. More than 65% of reducing sugar yield with 90.1% of glucose selectivity was achieved at 50 oC, pH=4.8 for 72 h (1200 r/min) with cellulase I of 7.5 FPU/g substrate and cellulase II of 5 FPU/g substrate.
Biodiesel production from waste cooking oils over SO42-/Zr-SBA-15 catalyst was successfully carried out and investigated. SO42-/Zr-SBA-15 catalyst was prepared by one-step process using anhydrous zirconium nitrate as zirconium resource, and endowed with the strong Lewis acid sites formed by supporting the zirconium species onto the SBA-15 surface. The asprepared SO42-/Zr-SBA-15 showed excellent triglyceride conversion efficiency of 92.3% and fatty acid methyl esters (FAME) yield of 91.7% for the transesteriffication of waste cooking oil with methanol under the optimized reaction conditions: the methanol/oil molar ratio of 30, the reaction temperature of 160 oC, the reaction time of 12 h and 10wt% of catalyst. It was noticed that the as-prepared SO42-/Zr-SBA-15 materials with the higher area surface of mesoporous framework and the surface acidity displayed excellent stability and reusability, maintaining high FAME yield of (74±1)% after seven runs of reaction.
Polyurethane-conjugated HgS nanocrystals with tunable sizes prepared by using biomimetic method. The obtained HgS nanoparticles with good dispersibility were characterized by Fourier transform infrared. Scanning electron microscopy are used to envisage the binding of nanoparticles with functional groups. The polyurethane molecules can control nucleation and growth of HgS crystals by binding on the surface of nanocrystals to stabilize nanoparticles. Quantum confinement effect of polyurethane-conjugated HgS nanocrystals was confirmed by UV-Vis spectra. The nanoparticles exhibit a well-defined emission feature at about 291 nm. The fluorescence results reveal that the PU/HgS nanoparticles film is sensitive to Ba2+, and a small amount of Ba2+ makes the emissions increase rapidly. The emission is hardly affected by other common ions in water. The nanocomposite film is possible to become a special sensor material for Ba2+.
Chinese Abstracts
2015, 28(3): 375-375.