2017 Vol. 30, No. 5

Content
Contents
2017, 30(5): .
Chinese abstract
Chinese Abstracts
2017, 30(5): I-Ⅱ.
Article
Transitions of the 6υ3 overtone band of 14N2 16O near 775 nm have been studied by continuous-wave cavity ring-down spectroscopy. Line positions and intensities were derived from a fit of the line shape using a hard-collisional profile. The line positions determined with absolute accuracy of 5×10-4 cm-1 allowed us to reveal finer ro-vibrational couplings taking place after J>14 except a strong anharmonic interaction identified by the effective Hamiltonian model. The absolute line intensities have also been retrieved with an estimated accuracy of 2% for a majority of the unblended lines. A new set of ro-vibrational and dipole moment parameters were derived from the experimental values. A comparison between the line positions and intensities of the 6υ3 band obtained in this work and those from previous studies is given.
A two-channel thermal dissociation cavity ring down spectroscopy (CRDS) instrument has been built for in situ, real-time measurement of NO2 and total RNO2 (peroxy nitrates and alkyl nitrates) in ambient air, with a NO2 detection limit of 0.10 ppbv at 1 s. A 6-day long measurement was conducted at urban site of Hefei by using the CRDS instrument with a time resolution of 3 s. A commercial molybdenum converted chemiluminescence (Mo-CL) instrument was also used for comparison. The average RNO2 concentration in the 6 days was measured to be 1.94 ppbv. The Mo-CL instrument overestimated the NO2 concentration by a bias of +1.69 ppbv in average, for the reason that it cannot distinguish RNO2 from NO2. The relative bias could be over 100% during the afternoon hours when NO2 was low but RNO2 was high.
The S(1D2)+CO(X1Σ+) product channel from photodissociation of OCS at 217 nm has been measured using the DC slice velocity map imaging (VMI) technique in combination with resonance enhanced multiphoton ionization (REMPI). Two diflerent REMPI intermediate states (1F3 and 1P1) and several pump-probe laser polarization geometries are used to detect the angular momentum polarization of the photofragmented S(1D2). The molecular- frame polarization parameters, as well as the laboratory-frame anisotropy parameters, for individual rotational states of co-fragment CO, are determined using two diflerent full quantum theories. The measured total kinetic energy release spectrum from photodissociation of OCS indicates two dissociation channels, corresponding to the fast and slow recoiling velocities of S(1D2), respectively. The slow channel is concluded to originate from an initial photoexcitation to the A(1A') state, followed by a non-adiabatic transition to the ground state. The fast channel is found to follow a coherent excitation to A(1A') and B(1A') states, where contributions of the two states are almost equal at 217 nm. The determined alignment and anisotropy parameters further indicate that the slow channel follows an incoherent excitation, while the fast channel follows a coherent excitation to A(1A') and B(1A') states with a phase di erence of π/2.
The Raman and infrared spectra of all-trans-astaxanthin (AXT) in dimethyl sulfoxide (DMSO) solvent were investigated experimentally and theoretically. Density functional cal-culations of the Raman spectra predict the splitting of the υ1 band into υ1-1 and υ1-2 compo-nents. The absence of splitting in Raman experimental spectra is ascribed to the competition between the two symmetric C=C stretching vibrations of the backbone chain. The υ1 band is very sensitive to the excitation wavelength: resonance excitation stimulates the higher-frequency υ1-2 mode, and off-resonance excitation corresponds to the lower-frequency υ1-1 mode. Analyses of the intramolecular hydrogen bonding between C=O and O-H in the AXT/DMSO system reveal that the C4=O1...H1-O3 and C4'=O2...H2-O4 bonds are strengthened and weakened, respectively, in the electronically excited state compared with those in the ground state. This result reveals significant variations of the AXT molecular structure in different electronic states.
The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy (FTIR) for the investigation of the crystal structure, thermal stability, redox behavior (temperature-programmed reduction/temperatureprogrammed re-oxidation) as well as the catalytic properties of Co3O4 thin films. The syntheses of Co3O4 were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm-1 (υ1) and 650 cm-1 (υ2) respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co3O4 spinel. The lattice stability limit of Co3O4 was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ1 and υ2 as a function of the temperature. Moreover, Co3O4 has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO2 and H2O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co3O4 follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.
Molecular interactions of the ternary mixtures of 1-butyl-3-methylimidazolium chloride ([C4C1im]Cl)-water-2,6-dimethoxyphenol (2,6-DMP, a phenolic monomer lignin model compound) were investigated in comparison with the [C4C1im]Cl-water binary systems through attenuated total reflection infrared spectroscopy. Results indicated that the microstructures of water and [C4C1im]Cl changed with varying mole fraction of [C4C1im]Cl (xIL) from 0.01 to 1.0. This change was mainly attributed to the interactions of [C4C1im]Cl-water and the self-aggregation of [C4C1im]Cl through hydrogen bonding. The band shifts of C-H on imidazolium ring and the functional groups in 2,6-DMP indicated that the occurrence of intermolecular interactions by different mechanisms (i.e., hydrogen bonding or π-π stacking) resulted in 2,6-DMP dissolution. In the case of xIL=0.12, the slightly hydrogen-bonded water was fully destroyed and [C4C1im]Cl existed in the form of hydrated ion pairs. Interestingly, the maximum 2,6-DMP solubility (238.5 g/100 g) was achieved in this case. The interactions and microstructures of [C4C1im]Cl-water mixtures influenced the dissolution behavior of 2,6-DMP.
We perform first-principles simulations on a type of two-dimensional metal-organic nanosheet derived from the recently reported manganese bis-dithiolene Mn3C12S12 [Nanoscale 5, 10404 (2013)] and manganese bis-diamine Mn3C12N12H12 [ChemPhysChem 16, 614 (2015)] mono-layers. By coordinating chalcogen (S or O) atoms and -NH- group to Mn atoms with trans- or cis-structures and preserving space inversion symmetry, four configurations of this type of nanosheet are obtained: trans-manganese dithiolene-diamine Mn3(C6S3N3H3)2, cis- manganese dithiolene-diamine Mn3(C6S6)(C6N6H6), trans-manganese dihydroxyl-diamine Mn3(C6O3N3H3)2, and cis-manganese dihydroxyl-diamine Mn3(C6O6)(C6N6H6). The ge- ometric con guration, electronic structure and magnetic properties of these metal-organic nanosheets are systematically explored by density functional theory calculations. The cal- culated results show that Mn3(C6S3N3H3)2, Mn3(C6O3N3H3)2 and Mn3(C6O6)(C6N6H6) monolayers exhibit half-metallicity and display strong ferromagnetism with Curie transition temperatures near and even beyond room temperature, and Mn3(C6S6)(C6N6H6) monolayer is a semiconductor with small energy gap and spin frustration ground state. The mechanisms for the above properties, especially in uences of diflerent groups (atoms) substitution and coordination style on the magnetism of the nanosheet, are also discussed. The predicted two-dimensional metal-organic nanosheets have great promise for the future spintronics ap-plications.
The irrationality of existing phase field model is analyzed and a modified phase-field model is proposed for polymer crystal growth, in which the parameters are obtained from real materials and very simple to use, and most importantly, no paradoxical parameters appeared in the model. Moreover, it can simulate different microstructure patterns owing to the use of a new different free energy function for the simulation of morphologies of polymer. The new free energy function considers both the cases of T<Tm and T≥Tm, which is more reasonable than that in published literatures that all ignored the T≥Tm case. In order to show the validity of the modified model, the finite difference method is used to solve the model and different crystallization morphologies during the solidification process of isotactic polystyrene are obtained under different conditions. Numerical results show that the growth rate of the initial secondary arms is obviously increased as the anisotropy strength increases. But the anisotropy strength seems to have no apparent effect on the global growth rate. The whole growth process of the dendrite depends mainly upon the latent heat and the latent heat has a direct effect on the tip radius and tip velocity of side branches.
Lithium ion battery has typical character of distributed parameter system, and can be described precisely by partial differential equations and multi-physics theory because lithium ion battery is a complicated electrochemical energy storage system. A novel failure prediction modeling method of lithium ion battery based on distributed parameter estimation and single particle model is proposed in this work. Lithium ion concentration in the anode of lithium ion battery is an unmeasurable distributed variable. Failure prediction system can estimate lithium ion concentration online, track the failure residual which is the difference between the estimated value and the ideal value. The precaution signal will be triggered when the failure residual is beyond the predefined failure precaution threshold, and the failure countdown prediction module will be activated. The remaining time of the severe failure threshold can be estimated by the failure countdown prediction module according to the changing rate of the failure residual. A simulation example verifies that lithium ion concentration in the anode of lithium ion battery can be estimated exactly and effectively by the failure prediction model. The precaution signal can be triggered reliably, and the remaining time of the severe failure can be forecasted accurately by the failure countdown prediction module.
Fe based oxides are considered as a promising catalyst for the oxygen evolution reaction (OER) due to their low cost and high stability. Here, based on density functional theory calculations, the electrocatalytic behaviors of pure and metal (Ni, Co) doped Fe-terminated Fe2O3(0001) are investigated. The potential-limiting step for OER is determined as the formation of O* by dehydrogenating surface hydroxyl and it is suggested that the doping enhances the catalytic activity of Fe2O3(0001) by reducing the free energy change of rate limiting step on doped Ni or Co atom. Especially, the calculated over-potential of Co-doped Fe2O3 (0001) surface is about 0.63 eV on Co site, which is comparable with the theoretical over-potential of 0.56 eV for RuO2.
Pd/C catalysts were prepared by deposited Pd nanoparticles (NPs) on different carbon supports including activated carbon (AC), graphite oxide (GO), and reduced graphite oxide (rGO) using sol-immobilization method. Through transmission electron microscopy, powder X-ray di raction, and X-ray photoelectron spectroscopy, the role of the carbon supports for the catalytic performances of Pd/C catalysts was examined in selective hydrogenation of acetylene. The results indicate that Pd/AC exhibited higher activity and selectivity than Pd/GO and Pd/rGO in the gas phase selective hydrogenation of acetylene. Thermal and chemical treatment of AC supports also have some effect on the catalytic performance of Pd/AC catalysts. The differences in the activity and selectivity of various Pd/C catalysts were partly attributed to the metal-support interaction.
Low-dimensional Bi2Fe4O9 nanosheets and microrods have been selectively prepared by a solvothermal method, from which the growth of the Bi2Fe4O9 crystals can be controlled by the variation of reaction conditions. Structure determination showed that the nanosheets are mainly exposed by {001} facets while the microrods are exposed by {110} facets. Ab- sorption spectra revealed that there are two bandgaps observed for both nanosheets (at 1.9 and 1.55 eV) and microrods (1.7 and 1.45 eV), and they both would be available for the sunlight photocatalysis e ciently due to the intensive absorption ability in a wide region. Photocatalytic investigation demonstrated that the overall photocatalytic performance of the microrods is prior to that of the nanosheets due to the variation of bandgaps and exposed facets. The present report provides a useful alternative strategy for the controlling growth of nanostructures and/or microcrystals besides the present demonstration of the Bi2Fe4O9 crystals with diflerent bandgaps and facets that would be able to tune the corresponding photocatalytic ability selectively.
We studied the dielectric properties of organosilicon-containing helical cyclopolymer PbMA which consists of PMMA main chains and tetramethyldisiloxane side rings. PbMA formed films with excellent uniformity through spin-coating onto highly n-doped silicon (n-Si) wafers for constructing devices of dielectric measurements, on which the dielectric properties and I-V characteristics of PbMA were studied. PbMA has a much lower dielectric constant (lower than 2.6) in the frequency range of 10-105 Hz, and better thermal stability than PMMA does. I-V data showed that the metal/PbMA/n-Si devices have different conducting directions, depending on whether Au or Al deposited over PbMA layers.
Novel Bi2MoO6/TiO2 heterojunction was fabricated by growing Bi2MoO6 nanosheets arrays on the vertically aligned TiO2 nanorods arrays via a two-step solvothermal method. The obtained Bi2MoO6/TiO2 hierarchical heterojunction showed excellent visible light photoelectrochemical performance. Compared with the pure TiO2 and Bi2MoO6, the photocurrent density of the heterojunction was increased 57 and 29 times, respectively. Furthermore, the hydrogen generation rate of the Bi2MoO6/TiO2 for photoelectrocatalytic water-splitting was about 6 times higher than that of the pure Bi2MoO6. The improved performance can be attributed to the synergistic effects of enhanced absorption of visible light, increase of migration rate and separation efficiency of photo-induced carriers.
Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in thickness. The Pt-Pd octahedral nanoframes were obtained through site-selected deposition of Pt atoms onto the edge sites of Pd octahedral seeds, followed by selective removal of the Pd octahedral cores via chemical etching. Due to that a combination of three-dimensional opens geometrical structure and Pt-skin surface compositional structure, the Pt-Pd octahedral nanoframes/C catalyst shows a mass activity of 1.15 A/mgPt towards oxygen reduction reaction, 5.8 times enhancement in mass activity relative to commercial Pt/C catalyst (0.20 A/mgPt). Moreover, even after 8000 cycles of accelerated durability test, the Pt-Pd octahedral nanoframes/C catalyst still exhibits a mass activity which is more than three times higher than that of pristine Pt/C catalyst.
In the present work, we reported a novel route for the conversion of lignocellulosic biomass (sawdust) to a high-value chemical of benzoic acid under atmospheric pressure. The trans- formation involved the catalytic pyrolysis of sawdust into aromatics, the decomposition of heavier alkylaromatics to toluene, and the liquid-phase oxidation of toluene-rich aromatics to benzoic acid. The production of the desired benzoic acid from the sawdust-derived aro- matics, with the benzoic acid selectivity of 85.1 C-mol% and nearly complete conversion of toluene, was achieved using the MnO2/NHPI catalyst at 100 ℃ for 5 h. The in uence of adding methanol on the catalytic conversion of sawdust to the core intermediate of toluene was also investigated in detail.
The interaction between bovine serum albumin (BSA) and the anionic 1.2-dipalmitoyl-snglycero- 3-(phospho-rac-(1-glycerol)) (sodium salt) (DPPG) phospholipid at different subphase pH values was investigated at air-water interface through surface pressure measurements and atomic force microscopy (AFM) observation. By analyzing surface pressure-mean molecular area (π-A) isotherms, the limiting molecular area in the closed packing state-the concentration of BSA (Alim-[BSA]) curves, the compressibility coefficient-surface pressure (CS-1-π) curves and the difference value of mean molecular area-the concentration of BSA (ΔA-[BSA]) curves, we obtained that the mean molecular area of DPPG monolayer became much larger when the concentration of BSA in the subphase increased at pH=3 and 5. But the isotherms had no significant change at different amount of BSA at pH=10. In addition, the amount of BSA molecules adsorbed onto the lipid monolayer reached a threshold value when [BSA]>5×10-8 mol/L for all pHs. From the surface pressure-time (π-t) data, we obtained that desorption and adsorption processes occurred at pH=3, however, there was only desorption process occurring at pH=5 and 10. These results showed that the interaction mechanism between DPPG and BSA molecules was affected by the pH of subphase. BSA molecules were adsorbed onto the DPPG monolayers mainly through the hydrophobic interaction at pH=3 and 5, and the strength of hydrophobic interaction at pH=3 was stronger than the case of pH=5. At pH=10, a weaker hydrophobic interaction and a stronger electrostatic repulsion existed between DPPG and BSA molecules. AFM images revealed that the pH of subphase and [BSA] could affect the morphology features of the monolayers, which was consistent with these curves. The study provides an important experimental basis and theoretical support to understand the interaction between lipid and BSA at the air-water interface.
Transparent, flexible electronic skin holds a wide range of applications in robotics, humanmachine interfaces, artificial intelligence, prosthetics, and health monitoring. Silver nanowire are mechanically flexible and robust, which exhibit great potential in transparent and electricconducting thin film. Herein, we report on a silver-nanowire spray-coating and electrodemicrostructure replicating strategy to construct a transparent, flexible, and sensitive electronic skin device. The electronic skin device shows highly sensitive piezo-capacitance response to pressure. It is found that micropatterning the surface of dielectric layer polyurethane elastomer by replicating from microstructures of natural-existing surfaces such as lotus leaf, silk, and frosted glass can greatly enhance the piezo-capacitance performance of the device. The microstructured pressure sensors based on silver nanowire exhibit good transparency, excellent flexibility, wide pressure detection range (0-150 kPa), and high sensitivity (1.28 kPa-1).