2014 Vol. 27, No. 5

Content
Article
The rovibrational state-selectivity in photoassociation (PA) is investigated for the ground electronic state of OH radical. The calculated results show that population can be transferred from continuum state to the target states through three-, four-, and nine-photon transitions by choosing suitable pulse parameters and initial collision energy. To control population transfer to a lower rovibrational state, a shorter pulse frequency has to be chosen and the photon number transferred to target state should be increased. In PA process, some associated OH radicals can be dissociated via intermediate and background states, whichdecreases the nal population of the target state.
The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric geometry at impact energy of 2.5 keV plus binding energy. The ionization bands have been assigned in detail via the high accuracy SACCI general-R method calculation and the experimental momentum profiles are compared with the theoretical ones calculated by Hartree-Fock and B3LYP/aug-cc-pVTZ(C,H)6-311G??(I). The spin-orbit coupling effect and intramolecular orbital interaction have been analyzed for the outermost two bands, which are assigned to the iodine 5p lone pairs, using NBO method and non-relativistic as well as relativistic calculations. It is found that both of the interactions will lead to the observed differences in electron momentum distributions. The experimental results agree with the relativistic theoretical momentum profiles, indicating that the spin-orbit coupling effect dominates in n-propyl iodide molecule.
We report an ab initio>/I> study of spectral properties of Ce3+ doped at Na+ site of the NaF crys-tal, with the charge imbalance compensated by two oxygen substitutions for fluoride (OF') in the first coordination shell or two sodium vacancies (VNa') in the second coordination sphere. Density functional theory calculations within the supercell model are first performed to op-timize the local structures of the charge-compensated Ce3+, based on which Ce-centered embedded clusters are constructed and wave function-based CASSCF/CASPT2/RASSI-SO calculations are carried out to obtain the energies of 4f1 and 5d1 levels. By comparing the calculated 4f→5d transition energies with experimental excitation spectra at low temper-atures, the lowest 4f→5d transition band peaked at 390 nm is assigned to the Ce3+ with charge compensation by two coordinating OF' substitutions, rather than to the Ce3+ with compensation by two VNa0 vacancies, as proposed earlier. The electronic reason for thelarge redshift (by ~8000 cm-1) of the lowest 4f→5d transition as induced by the two nearby OF' substitutions is analyzed in terms of the changes in the centroid shift and crystal-field splitting.
Based on density functional theory (DFT) calculations, we investigate the spin-related properties of spinless-hole injected organic molecule pentacene (Pc). DFT calculations reveal that there is spontaneous spin polarization in Pc when spinless-hole is injected. The chargeinduced magnetic moment of Pc increases linearly with the increasing of the extra hole charge amount and its maximum can be up to 1 μB per injected spinless-hole per Pc molecule. The magnetic moment is expected due to the injected unpaired charge. The injected hole will preferably ll the spin-splitted carbon pz orbitals, which makes the Pc molecule spin polarize.
Multi-walled carbon nanotubes (MWCNT) supported Cu-Co composite oxides catalysts were prepared by an ultrasonication treatment-aided impregnation method. The structure prop-erties of the catalysts were characterized by XRD, TEM, H2-TPR, XPS and Raman spectra, indicating the strong interactions between Cu and Co mixed oxides as well as between metal oxides and MWCNT support. The catalytic performance of CO removal in a H2-rich stream was examined. In contrast to the single Cu and Co catalyst, the unique performance was ob-served for Cu-Co composite catalysts, which features an unusual reaction pathway through the combination of CO preferential oxidation and CO methanation especially at high reac-tion temperature. The optimal catalyst with Cu/Co ratio of 1/8 can achieve the complete CO conversion in a wider temperature range of 150-250 oC under the space velocity as high as 120 L/(h·g), which demonstrates a promising catalyst for the e ective CO removal in a H2-rich stream.
{001} facets dominated single crystalline anatase TiO2 nanosheet array (TNSA) was synthe-sized through an optimized organic solvothermal route on uorine-doped tin oxide substrate. The field emission scanning electron microscopy images and X-ray diffraction patterns re-vealed that the {001} synthesized facets dominated TNSA exhibited much higher orientation than that synthesized by hydrothermal route. The TNSAs were loaded with Pt nanoparti-cles in uniformly size by using a photodecomposition method, which were further con rmed by high resolution transmission electron microscopy (HRTEM). The HRTEM images also revealed that Pt nanoparticles preferred to deposit on {001} facets. With loading of Pt nanoparticles, the optical absorbance was significantly enhanced, while the photolumines-cence (PL) was inhibited. The photocatalytic activity of TNSA was signi cantly improved by Pt loading and reached the maximum with optimal amount of Pt loading. The optimal amount of Pt on {001} facets is far less than that on TiO2 nanoparticles, which may be attributed to the specific atom structure of reactive {001} facets.
Phytic acid (PA) conversion coating on AZ31 magnesium alloy is prepared by a deposition method. pH influences on the formation process, microstructure and properties of the conversion coating are investigated. Electrochemical tests including polarization curve and electrochemical impedance spectroscopy are used to examine the corrosion resistance, and scanning electron microscopy is used to observe the microstructure. The chemical nature of conversion coating is investigated by energy dispersive spectroscopy. And thermodynamic method is used to analyze the optimum pH. The results show that PA conversion coating can improve the corrosion resistance of AZ31 Mg alloy. The maximum efficiency achieves 89.19% when the AZ31 Mg alloy is treated by PA solution with pH=5. It makes the corrosionpotential of sample shift positively about 156 mV and corrosion current density is nearly an order of magnitude less than that of the untreated sample. The thermodynamic analysis shows that the corrosion resistance of PA coatings is affected by not only the concentration of PA ion and Mg2+ but also the release rate of hydrogen.
Methanol oxidation reaction (MOR) at Pt and Pt electrode surface deposited with various amounts of Ru (denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML) in 0.1 mol/L HClO4+0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that (i) CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V (vs. RHE); (ii) at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; (iii) MOR activity decreases in the order of Pt0.73Ru0.27>Pt0.56Ru0.44>Pt0.83Ru0.17>Pt; (iv) at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/(site sec). Suggestions for further improving of PtRu catalysts for MOR are provided.
Single source molecular precursors (SSPs) provide an opportunity to get control over the microstructure of nanomaterials at atomic level. A SSP was designed and developed for the synthesis of ZnO/TiO2 nanocomposite by sol gel method. In a typical synthe-sis process, a bimetallic molecular compound with chemical formula [Cl2TiZn(dmae)4] (dmae=dimethylaminoethanol) was synthesized and its chemical composition was deter-mined by elemental analysis. The obtained compound has shown excellent solubility in common organic solvents, a prerequisite for its use in sol gel method as SSP. The SSP ob-tained was controllably hydrolyzed by adding equimolar amount of water using ethanol as solvent to get ZnO/TiO2 nanocomposite gel. The resulting gel was precipitated at pH=9 and sintered at 200 oC (T200), 400 oC (T400), and 600 oC (T600). The XRD analyses have shown that the as synthesized (non-sintered, T00) powder was amorphous. However, the crystallinity improved upon sintering, and the XRD analyses revealed that the resulting nanomaterials were composed of mixed oxides i.e., ZnO and TiO2. The ZnO was in wurtzite (hexagonal) while the TiO2 was in brookite (orthorhombic) phase. The increase in particlesize was further confirmed from BET analysis and SEM micrographs. The IR spectra ob-tained for the resulting powder have shown the peculiar vibrational bands for Zn-O and Ti-O. Furthermore, the IR spectra revealed that the non-sintered ZnO/TiO2 nanocomposite had significant number of OH group which was removed upon sintering. The photocatalytic activities of the ZnO/TiO2 nanocomposites were tested. All the samples have shown good photocatalytic activities. However, the T400 has shown higher activity than the T00, T200, and T600. The higher photocatalytic activity of T400 than T00, T200, and T600 may be due to improved crystallinity which ensures efficient grain boundary interfaces.
Bamboo-structured boron nitride (BN) nanotubes with thorn-like morphology were synthe-sized by thermal chemical reaction using amorphous boron powders and NiO nanoparticles as precursors under the flow of NH3 at 1100 oC. The structural and morphological charac-teristics of BN nanotubes were investigated by X-ray diraction and transmission electron microscopy. The results showed that the thorn-like nanostructures attaching to the stems of bamboo-structured BN nanotubes were the hexagonal BN nano akes. Based on the diffu-sion of solid B and vapor B2O2, a possible growth mechanism of these novel thorn-like BN nanotubes was primarily proposed.
Due to depletion interactions, a few of colloidal spheres will be packed into cluster or clusters, even a phase transition may take place if the volume fraction of system is large enough. In a binary colloidal system, if the mole fraction of one component is very small, then it can be taken as the impurity of the other component. In this work, the effect of impurity on critical conditions of colloidal cluster nucleation was studied by Carnahan-Starling state equation and the principle of entropy maximum. The results show that, even the mole fraction of small-spheres is very small, the critical volume fraction is obvious smaller than that of one component system, so the influence on critical volume fraction from impurity is very huge and cannot be ignored. In addition, it is also found that, the larger the volume fraction of the system is, the larger cluster density can be packed, however, the critical size of nucleating cluster is almost independent of the density of the cluster.
A modified seeded growth process of silica particles with a continuous addition of tetraethyl orthosilicate (TEOS) was presented to control the diameter of silica particles. The diameter of particles was monitored by dynamic light scattering to control the addition of TEOS. The increase in the diameter of the silica particles with time and the addition of TEOS was investigated. The diameter of silica seeds increased from 193 nm to 446 nm in 4 h. The final diameter of silica particles was tailored within the range of ±5 nm to the target diameter. Silica particles with diameter of 446 nm were synthesized and assembled into photonic crystals with a pseudo band gap centered at just 1000 nm. The feasibility and practicability of this modified seeded growth process was verified.
Mesh-like Bi2MoO6 product was successfully synthesized by a hydrothermal method without using any surfactant or template. The pH value played an important role in the formation of this morphology. The as-prepared mesh-like Bi2MoO6 sample exhibited excellent visible-light-driven photocatalytic e ciency. The photocatalytic activity of the mesh-like Bi2MoO6 sample was much higher than that of bulk Bi2MoO6 sample prepared by solid-state reac-tion. Di erence in the photocatalytic activities of the mesh-like Bi2MoO6 sample and bulk Bi2MoO6 sample was further investigated.
A series of bifunctional catalysts composed of a component for higher alcohol synthesis (Cu-CoMn oxides, CCM) and an acidic zeolite (SAPO-34, ZSM-5, Y, MCM-41) were prepared for production of liquid hydrocarbon directly from a bio-syngas through a one-stage pro-cess. The effects of zeolite type, zeolite content, Si/Al ratio and preparation method on catalyst texture and its reaction performance were investigated. Higher selectivities and yields of liquid products were obtained by using bifunctional catalysts. The yields of liquid hydrocarbons decreased in the order CCM-ZSM-5>CCM-SAPO-34>CCM-Y>CCM-MCM-41. CCM-ZSM-5 (20wt%, Si/Al=100) prepared by coprecipitation method displayed the optimal catalytic performance with the highest CO conversion (76%) and yield of liquid products (30%). The catalysts were characterized by N2 adsorption/desorption, NH3-TPD, XRD, and H2-TPR analysis. The results showed that higher speci c surface areas and pore volumes of bifunctional catalysts were achieved by adding zeolites into CuCoMn precursors. Medium pore dimension and moderate acidity in CCM-ZSM-5 were observed, which proba-bly resulted in its excellent reaction performance. Additionally, a higher number of weaker acid sites (weak and/or medium acid sites) were formed by increasing ZSM-5 content in CCM-ZSM-5 or decreasing Si/Al ratio in ZSM-5. It was also seen that metal dispersion was higher and reducibility of metal ions was easier on the CCM-ZSM-5 catalyst prepared by coprecipitation. The higher alcohols-to-hydrocarbon process provides a promising route to hydrocarbon fuels via higher alcohols from syngas or biobased feedstocks.
Characterization of electric properties of nanomaterials usually involves fabricating field effect transistors (FET) and deriving materials properties from device performances. However, the quality of electrode contacts in FET devices heavily influences the device performance, which makes it difficult to obtain the intrinsic electric properties of nanomaterials. Dielectric force microscopy (DFM), a contactless method developed recently, can detect the low-frequency dielectric responses of nanomaterials without electric contact, which avoids the influence of electric contact and can be used to study the intrinsic conductivity of nanomaterials.Here we study the influences of surface adsorbates on the conductivity of ZnO nanowires (NWs) by using FET and DFM methods. The conductivity of ZnO NW is muchlarger in N2 atmosphere than that in ambient environment as measured by FET device, which is further proven by DFM measurement that the ZnO NW exhibits larger dielectric response in N2 environment, and the influence of electrode contacts on measurement can be ruled out. Based on these results, it can be concluded that the adsorbates on ZnO NW surface highly influence the conductivity of ZnO NW rather than the electrode contact. This work also verifies the capability of DFM in measuring electric properties of nanomaterials.
Dendrimer-like amphiphilic copolymer is a kind of three-dimensional spherical structure polymer. An amphiphilic dendrimer-like diblock copolymer, PEEGE-G2-b-PEO(OH)12, constituted of a hydrophobic poly(ethoxyethyl glycidol ether) inner core and a hydrophilic poly(ethylene oxide) outer layer, has been successfully synthesized by the living anionic ring-opening polymerization method. The intermediates and targeted products were charac-terized with 1H NMR spectroscopy and gel permeation chromatography. The application on drug delivery of dendrimer-like diblock copolymer PEEGE-G2-b-PEO(OH)12 using DOX as a model drug was also studied. The drug loading content and encapsulation e ciency were found at 13.07% and 45.75%, respectively. In vitro release experiment results indicated that the drug-loaded micelles exhibited a sustained release behavior under acidic media.
An electron transporting material of TFTTP (4-(5-hexylthiophene-2-yl)-2,6-bis(5-trifluoromethyl)thiophen-2-yl)pyridine) was investigated as a cathode buffer layer to enhance the power efficiency of organic solar cells (OSCs) based on subphthalocyanine and C60. The overall power conversion efficiency was increased by a factor of 1.31 by inserting the TFTTP interfacial layer between the active layer and metallic cathode. The inner mechanism responsible for the performance enhancement of OSCs was systematically studied with the simulation of dark diode behavior and optical field distribution inside the devices as well as the characterization of device photocurrent. The results showed that the TFTTP layer could significantly increase the built-in potential in the devices, leading to the enhanced dissociation of charge transfer excitons. In addition, by using TFTTP as the buffer layer, a better Ohmic contact at C60/metal interface was formed, facilitating more efficient free charge carrier collection.
The MoOx/AuNPs composite film modified glassy carbon electrode was fabricated by electro-depositing simultaneously gold nanoparticles and molybdenum oxides using cyclic voltammetry. The morphology and topography of the MoOx/AuNPs composite were char-acterized by scan electron microscopy and X-ray photoelectron spectroscopy respectively, and the electrocatalytic oxidation of glucose at the MoOx/AuNPs composite film was inves-tigated and analyzed in detail. It was shown that the MoOx/AuNPs composite was of strong electrocatalytic activity towards oxidation of glucose as well as other saccharides, so that an attempt was made for direct voltammetric determination of glucose. Then the positive scan polarization reverse catalytic voltammetry was proposed for the first time. Based on this method, the pure oxidation current was extracted by subtraction of the blank current in the reverse scan. The current sensitivity was enhanced tremendously and the signal to noise ra-tio was improved adequately. The electrocatalytic oxidation of glucose at the MoOx/AuNPs modified electrode was performed in alkaline medium, a wide linear range from 0.01 mmol/L to 4.0 mmol/L of glucose, a higher current sensitivity of 2.35 mA/(mmol/L·cm2), and a lower limit of detection of 9.01 μmol/L (at signal/noise=3) were achieved. In addition, the electrocatalytic oxidation of other saccharides such as lactose, fructose and sucrose was also evaluated.
UV-curable polyurethane prepolymer and photoinitiator 1173 were facilely encapsulated in a poly(urea-formaldehyde) shell, which was in situ formed by the polymerization of formalde-hyde and urea in an oil-in-water emulsion. The diameters of the microcapsules ranged from 118 μm to 663 μm depending on agitation speed, and were obtained via optical mi-croscopy and scanning electron microscopy analyses. The encapsulation percent and the yield of microcapsules prepared at the agitation speed of 600 r/min can reach 97.52wt% and 65.23wt%, respectively. When the water-borne polyurethane (WPU) coating embedded with the prepared microcapsules were scratched, the healing agent could be released from rup-tured microcapsules and lled the scribed region. The excellent anticorrosion properties of the WPU coating embedded with the prepared microcapsules were con rmed by the results obtained from both electrochemical impedance spectroscopy and Tafel curves.
In this work, supramolecular fixation of three amines, including aniline, ethylenediamine, and diethylamine, using cobalt tetraphenylporphyrin (CoTPP) for SO2 removal was studied using UV-Vis and fluorescence measurements. The UV-Vis spectra showed that increasing amines concentrations resulted in bathochromic shift for CoTPP Soret absorption band (B band). Once SO2 was introduced, it competed with CoTPP for aniline, ethylenediamine, and diethylamine, which eventually led to the release of CoTPP and the change of solution colour/absorption band. After that, the CoTPP was regenerated and got back to the first state. The fluorescence spectra offered that CoTPP interacted with aniline, ethylenediamine, and diethylamine to form 1:1 molecular adducts. The interactions of CoTPP with aniline, ethylenediamine, and diethylamine were entropy-driven. The interaction of CoTPP with aniline and diethylamine was endothermic, and that with ethylenediamine was exothermic. Ethylenediamine presented a stronger binding constant value for CoTPP, so it was considered as a potential agent for SO2 removal.
Chinese abstract