2017 Vol. 30, No. 1

Content
Contents
2017, 30(1): 0-0.
Chinese abstract
Chinese Abstracts
2017, 30(1): I-Ⅱ.
Article
Photocatalysis of 2-propanol on A-TiO2(101) has been investigated using a temperature programed desorption method with 266 nm laser light. A clear mechanism is proposed for photodissociation of 2-propanol on A-TiO2(101). Acetone product on five coordinate Ti4+ sites is formed in a stepwise manner in which the O-H dissociation proceeds first and then followed by secondary C-H dissociation of 2-propanol while H atoms are transferred to the adjacent bridge bond oxygen (BBO) sites. Low temperature water is formed in a thermally driven process via H-atom on BBO in exchange with isopropyl groups of molecule 2-propanol, while isopropyl radical desorbs at high temperature during the TPD process. The observation demonstrates the prospect of TiO2 as a photocatalyst for degradation of organics.
The IR absorption, visible excited normal Raman, and UV-excited near-resonant Raman (UVRR) spectra of 1,1'-binaphthyl-2,2'-diamine (BINAM) were measured and analyzed. Density functional theory calculations were carried out to investigate its vibrational frequencies, infrared absorption, normal Raman, and near-resonance Raman intensities. The observed Raman and IR bands of BINAM were assigned with respect to the local vibrations of substituted 2-naphthylamine. Several Raman bands of BINAM were found selectively enhanced in the UVRR in comparison with the normal Raman spectrum. Possible excited state geometry distortion was discussed based on the resonance Raman intensity analysis.
The time-dependent wave-packet method was employed to calculate the first full-dimensional state-to-state differential cross sections (DCS) for the title reaction with D2O in the ground and the first symmetric (100) and asymmetric stretching (001) excited states. The calculated DCSs for these three initial states are strongly backward peaked at low collision energies. With the increase of collision energy, these DCSs become increasingly broader with the peak position shifting gradually to a smaller angle, consistent with the fact that the title reaction is a direct reaction via an abstraction mechanism. It is found that the (100) and (001) states not only have roughly the same integral cross sections, but also have essentially identical DCS, which are very close to that for the ground state at the same total energy of reaction. The reaction produces a small fraction of OD in the v=1 state, with the population close to the relative reactivity between the ground and vibrationally excited states, therefore confirming the experimental result of Zare et al. and the local mode picture[J. Phys. Chem. 97 , 2204 (1993)]. Unexpectedly, the stretching excitation reduces the rotation excitation of product HD at the same total energy.
Does the halogen bonding interaction co-exist in liquid when it competes with the hydrogen bonding interaction? The classical molecular dynamics simulations for the solvation properties of ClF molecule in water are performed with the Lennard-Jones plus Coulomb electrostatic potential parameters that are optimized with ab initio interaction energy calculations for the pre-reactive H2O…ClF complex. We find that the halogen bonding interactions occur between O and Cl atoms and have the comparable strength and population with respect to the hydrogen bonding interactions of Cl…H.
Picene, which attracts the great interest of researchers, not only can be used to fabricate thin film transistors with high hole mobilities, but also is the parent material of a new type organic superconductor. Here, we investigate the electronic properties of individual picene molecules directly adsorbed on Cu(111) surface by a combination of experimental scanning tunneling microscopy/spectroscopy measurements and theoretical calculations based on the density functional theory. At low coverage, the picene molecules exhibit mono-dispersed adsorption behavior with the benzene ring planes parallel to the surface. The highest occupied state around-1.2 V and the lowest unoccupied state around 1.6 V with an obvious energy gap of the singly adsorbed picene molecule are identified by the dI/dV spectra and maps. In addition, we observe the strong dependence of the dI/dV signal of the unoccupied states on the intramolecular positions. Our first-principles calculations reproduce the above experimental results and interpret them as a specific molecule-substrate interaction and energy/spatial distributions of hybrid states mainly derived from different molecular orbitals of picene with some intermixing between them. This work provides direct information on the local electronic structure of individual picene on a metallic substrate and will facilitate the understanding the dependence of electron transport properties on the coupling between molecules and metal electrodes in single-molecule devices.
Graphite-like carbon nitride (g-C3N4) based heterostrutures has attracted intensive attention due to their prominent photocatalytic performance. Here, we explore the g-C3N4/SnS2 coupling effect on the electronic structures and optical absorption of the proposed g-C3N4/SnS2 heterostructure through performing extensive hybrid functional calculations. The obtained geometric structure, band structures, band edge positions and optical absorptions clearly reveal that the g-C3N4 monolayer weakly couples to SnS2 sheet, and forms a typical van der Waals heterojunction. The g-C3N4/SnS2 heterostructure can effectively harvest visible light, and its valence band maximum and conduction band minimum locate in energetically favorable positions for both water oxidation and reduction reactions. Remarkably, the charge transfer from the g-C3N4 monolayer to SnS2 sheet leads to the built-in interface polarized electric field, which is desirable for the photogenerated carrier separation. The built-in interface polarized electric field as well as the nice band edge alignment implys that the g-C3N4/SnS2 heterostructure is a promising g-C3N4 based water splitting photocatalyst with good performance.
Theoretical calculations have been carried out to investigate the possible dissociation channels of isoprene. We focus on the major fragment ions of C5H7+,C5H5+,C4H5+,C3H6+,C3H5+,C3H4+,C3H3+ and C2H3+, which were observed experimentally from the isoprene dissociative photoionization. The energy calculations were performed with the CBS-QB3 model. All the geometries and energies of the fragments, intermediates and transition states involved in the dissociations channels were determined. Finally, the mechanisms of the dissociation pathways were discussed on the comparison of theoretical and experimental results.
Charge density distribution in ampicillin trihydrate was investigated experimentally. Results were compared with the quantum calculations using density functional theory. The charge derived properties including Mulliken atomic charges, dipole moment, and molecular electrostatic potential were calculated. The multipole analysis was done for the refinement of experimental population parameters. The structure factors obtained from multipole treatment were used for the construction of Fourier maps. Topological properties of the charge distribution were discussed and the characteristics of (3,-1) critical points were analyzed.
The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption (TPA) processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.
Developing a widely-used reactive force field is meaningful to explore the fundamental reaction mechanism on gas-surface chemical reaction dynamics due to its very high computational efficiency. We here present a study of hydrogen and its deuterated molecules dissociation on Pd surfaces based on a full-dimensional potential energy surface (PES) constructed by using a simple second moment approximation reactive force field (SMA RFF). Although the descriptions of the adsorbate-substrate interaction contain only the dissociation reaction of H2/Pd(111) system, a good transferability of SMA potential energy surface (PES) is shown to investigate the hydrogen dissociation on Pd(100). Our simulation results show that, the dissociation probabilities of H2 and its deuterated molecules on Pd(111) and Pd(100) surfaces keep non-monotonous variations with respect to the incident energy Ei, which is in good agreement with the previous ab initio molecular dynamics. Furthermore, for the oriented molecules, the dissociation probabilities of the oriented H2 (D2 and T2) molecule have the same orientation dependence behavior as those oriented HD (HT and DT) molecules.
The irradiation-induced sputtering and the structural damage at tungsten surface are investigated by using molecular dynamics simulations at the level of quantum mechanics. Our simulations indicate that the sputtered atoms appear when the energy of incident primary knock-on atom (PKA) is more than 200 eV and the incident angle of the PKA is larger than 65°. Meanwhile, the irradiation-induced vacancies are less when the incident angle of PKA is in the range of 45°-65°. So, the optimum incident angles of PKA are suggested to reduce the irradiation-induced damage of the W surface. Furthermore, we find that the interstitials contained in the systems accelerate the sputtering whereas the intrinsic vacancies suppress the sputtering when the PKA is near the defects.
Electron inelastic mean free path (IMFP) is an important parameter for surface chemical quantification by surface electron spectroscopy techniques. It can be obtained from analysis of elastic peak electron spectroscopy (EPES) spectra measured on samples and a Monte Carlo simulation method. To obtain IMFP parameters with high accuracy, the surface excitation effect on the measured EPES spectra has to be quantified as a surface excitation parameter (SEP), which can be calculated via a dielectric response theory. However, such calculated SEP does not include influence of elastic scattering of electrons inside samples during their incidence and emission processes, which should not be neglected simply in determining IMFP by an EPES method. In this work a Monte Carlo simulation method is employed to determine surface excitation parameter by taking account of the elastic scattering effect. The simulated SEPs for different primary energies are found to be in good agreement with the experiments particularly for larger incident or emission angles above 60° where the elastic scattering effect plays a more important role than those in smaller incident or emission angles. Based on these new SEPs, the IMFP measurement by EPES technique can provide more accurate data.
Various Au/GO catalysts were prepared by depositing Au nanoparticles on thermally- and chemically-treated graphite oxide (GO) supports using a sol-immobilization method. The surface chemistry and structure of GO supports were characterized by a series of analytical techniques including X-ray photoelectron spectroscopy, temperature-programmed desorption and Raman spectroscopy. The results show that thermal and chemical treatments have large influence on the presence of surface oxygenated groups and the crystalline structure of GO supports. A strong support effect was observed on the catalytic activity of Au/GO catalysts in the liquid phase aerobic oxidation of benzyl alcohol. Compared to the amount and the type of surface oxygen functional groups, the ordered structure of GO supports may play a more important role in determining the catalytic performance of Au/GO catalysts.
We have investigated the structure, optical and magnetic properties of ferroelectric KNb1-xFexO3-δ (X=0, 0.01, 0.03, 0.05, 0.10, 0.15, 0.20, 0.25) synthesized by a traditional solid-state reaction method. According to the X-ray diffraction and the results of Rietveld refinement, all the samples maintain orthorhombic distorted perovskite structures with Amm2 space group without any secondary phase, suggesting the well incorporation of Fe ions into the KNbO3 matrix. With the increase of Fe concentration, the band gap of each sample is decreased gradually, which is much smaller than the 3.18 eV band gap of pure KNbO3. Through X-ray photoelectron spectrum analysis, the increased density of oxygen vacancy and Fe ions may be responsible for the observed decrease in band gap. Compared with the pure KNbO3, Fe doped samples exhibit room-temperature weak ferromagnetism. The ferromagnetism in KNb1-xFexO3-δ with low-concentration dopants (x=0.01-0.10) can be attributed to the bound magnetic polaron mediated exchange. The enhancement of magnetism for the high-concentration (x=0.10-0.20) doped samples may arise from the further increase of magnetic Fe ions.
The pure Cr2O3 coated Li4Ti5O12 microspheres were prepared by a facile and cheap solutionbased method with basic chromium(III) nitrate solution (pH=11.9). And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr2O3 works as an adhesive interface to strengthen the connections between Li4Ti5O12 particles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, LixCr2O3, formed by the lithiation of Cr2O3, can further stabilize Li7Ti5O12 with high electric conductivity on the surface of particles. While in the acid chromium solution (pH=3.2) modification, besides Cr2O3, Li2CrO4 and TiO2 phases were also found in the final product. Li2CrO4 is toxic and the presence of TiO2 is not welcome to improve the electrochemical performance of Li4Ti5O12 microspheres. The reversible capacity of 1% Cr2O3-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At-20℃, its reversible specific capacity was still as high as 118 mAh/g.
Films of polypyrrole/graphene on titanium mesh were prepared by electrochemical reduction of the fresh dried foam films of graphene oxide followed by an electrochemical polymerization of pyrrole. The as-obtained composite had highly surface area, conductivity, and could be used as the electrode for supercapacitors, especially directly used as the active materials in free of binders while the Ti mesh worked as the collector. Plenty of polypyrrole nanoparticles formed on the surface of reduced graphene film, and some fiber-like aggregates could be formed during the polymerization, which worked as the material for pseudo-capacitance. The specific capacitance of the supercapacitor reached 400 F/g and showed high stability with retaining capacitance of 82% after 5000 cycles, indicating that the nanocomposite is a suitable active material for supercapacitors.
Pyoverdine is one of the siderphores excreted by Pseudomonas aeruginosa that can help microbe to uptake iron in vitro. To determine the effect of pyoverdine chelating with iron, we purified the free pyoverdine and applied the dynamic laser light scattering (DLS) to detect the interaction between the pyoverdine and ferric hydroxide. The real-time DLS data analysis indicated that pyoverdine can directly combine with Fe(OH)3 to form complexes and these substances are gradually degraded by themselves then completely disappeared. In our experiment, we have demonstrated that pyoverdine may not only chelate ferric ion but also availably dissolve ferric hydroxide which assists bacteria to survive in iron-deficient environments.