Table of contents

Based on previous laser-induced fluorescence excitation spectroscopy work, the vibrational constants of neutral FeS in the X⁵Δ electronic state were obtained by directly mapping the ground-state vibrational levels up to v''=3 using conventional laser-induced dispersed fluorescence spectroscopy. The vibrational frequency of FeS(X⁵Δ) (518±5 cm⁻¹) agrees well with that reported in a recent PES measurement (520±30 cm⁻¹) [J. Phys. Chem. A 107, 2821 (2003)] which is the only one prior experimental vibrational frequency value for the ⁵Δ state of FeS. Careful comparisons of our experimental results and those documented in the literature (mainly from theoretical predictions) suggest that the ground state of FeS is ⁵Δ state.

The dynamics of the Cl+SiH₄ reaction has been studied using the universal crossed molecular beam method. Angular resolved time-of-flight spectra have been measured for the channel SiH₃Cl+H. Product angular distributions as well as energy distributions in the center-of-mass frame were determined for the channel. Experimental results show that the SiH₃Cl product is mainly backward scattered relative to the Cl atom beam direction, suggesting that the channel takes place via a typical S_N2 type reaction mechanism.

Absorption spectra of jet-cooled PH2 radicals were recorded in the wavelength range of 465–555 nm using cavity ringdown spectroscopy. The PH2 radicals were produced in a supersonic jet by pulsed direct current discharge of a mixture of PH3 and SF6 in argon. Seven vibronic bands with fine rotational structures have been observed and assigned as 000, 2n0, and 2n1 (n = 1–3) bands of the Ã2A1−2B1 electronic transition. Rotational assignments and rotational term values for each band were re-identified, and the molecular parameters including rotational constants, centrifugal distortion constants, and spin-rotation interaction constants were also improved with reasonably high precision. In addition, large perturbations observed in each quantum number of total angular momentum of the a axis level of the excited vibronic states were briefly discussed.

The G3 and CBS-QB3 theoretical methods are employed to study the decomposition of CF₃OH into FCFO and HF by water, water dimmer, and ammonia. The decomposition of CF₃OH into FCFO and HF is unlikely to occur in the atmosphere due to the high activated energy of 88.7 kJ/mol at the G3 level of theory. However, the computed results predict that the barrier for unimolecular decomposition of CF₃OH is decreased to 25.1 kJ/mol from 188.7 kJ/mol with the aid of NH₃ at the G3 level of theory, which shows that the ammonia play a strong catalytic effect on the split of CF₃OH. In addition, the calculated rate constants show that the decomposition of CF₃OH by NH₃ is faster than those of H₂O and the water dimmer by 10⁹ and 10⁵ times respectively. The rate constants combined with the corresponding concentrations of these species demonstrate that the reaction CF₃OH with NH₃ via TS4 is of great importance for the decomposition of CF₃OH in the atmosphere.

Nearly free electron (NFE) state has been widely studied in low dimensional systems. Based on first-principles calculations, we identify two types of NFE states in graphane nanoribbon superlattice, similar to those of graphene nanoribbons and boron nitride nanoribbons. Effect of electron doping on the NFE states in graphane nanoribbon superlattice has been studied, and it is possible to open a vacuum transport channel via electron doping.

Poly(silanylenediethynylanthracene) (PSDEA) exhibits a hole-transporting ability experimentally. In order to simulate the property of PSDEA, a series of silanylenediethynylanthracene oligomers were designed. The structures of these oligomers were optimized by using density function theory at B3LYP/6-31G(d) level. The energy gaps of the oligomers decrease with the increase in the chain length. The energy gaps of the oligomers also decrease in the presence of the electron-withdrawing group on the anthracene ring. The ¹³C chemical shifts and nucleus independent chemical shifts (NICS) at the anthracene ring center in the oligomers were calculated at B3LYP/6–31G level. The chemical shifts of the carbon atoms connected with the nitryl group changed upfield, compared with those of the carbon atoms without the nitryl group. The aromaticity at the anthracene ring center decreases in the presence of the electron-withdrawing group, whereas increases with the increase in the number of the silanylene units. The most sensitive location for calculating the NICS values is 0.1 nm above the anthracene plane.

We take the contribution of all valence electrons into consideration and propose a new valence electrons equilibration method to calculate the equalized electronegativity including molecular electronegativity, group electronegativity, and atomic charge. The ionization potential of alkanes and mono-substituted alkanes, the chemical shift of ¹H NMR, and the gas phase proton affinity of aliphatic amines, alcohols, and ethers were estimated. All the expressions have good correlations. Moreover, the Sanderson method and Bratsch method were modified on the basis of the valence electrons equilibration theory. The modified Sanderson method and modified Bratsch method are more effective than their original methods to estimate these properties.

A novel bifunctional blue-light material, 9-(pyren-1-yl)-9H-carbazole (CzPy), has been synthesized and its structure is identified by electron ionization mass spectrometry, ¹H NMR, and element analysis. The absorption, photoluminescence spectra and thermal properties were studied, results showed that CzPy was stable under ambient conditions with a blue-light emission (461 nm). Additionally, its electroluminescence properties were characterized with four different devices. Results indicated a maximum luminous efficiency reached 1.56 cd/A and maximum luminance up to 3526 cd/m² at 10 V with commission international De L' Eclairage coordinates of (0.20, 0.24) when it was used as emitter. Furthermore, CzPy also indicated hole-transporting ability.

We investigate the electronic and magnetic properties of the diluted magnetic semiconductors Zn_1−xMn_xS(001) thin films with different Mn doping concentrations using the total energy density functional theory. The energy stability and density of states of a single Mn atom and two Mn atoms at various doped configurations and different magnetic coupling state were calculated. Different doping configurations have different degrees of p-d hybridization, and because Mn atoms are located in different crystal-field environment, the 3d projected densities of states peak splitting of different Mn doping configurations are quite different. In the two Mn atoms doped, the calculated ground states of three kinds of stable configurations are anti-ferromagnetic state. We analyzed the 3d density of states diagram of three kinds of energy stability configurations with the two Mn atoms in different magnetic coupling state. When the two Mn atoms are ferromagnetic coupling, due to d-d electron interactions, density of states of anti-bonding state have significant broadening peaks. As the concentration of Mn atoms increases, there is a tendency for Mn atoms to form nearest neighbors and cluster around S. For such these configurations, the antiferromagnetic coupling between Mn atoms is energetically more favorable.

Electrochemical copolymerization of phenol and aniline was achieved on 304 stainless steel anodes in neutral water solution with an electrolyte of Na₂SO₄O₄. Compared with pit corrosion potential of different copolymer coatings, the best solution composition was 0.09 mol/L phenol and 0.01 mol/L aniline. Through infrared spectrum analysis, polyaniline structure was proved in phenol-aniline copolymer, as well as more side chains. Scanning electron microscope was used to analyze microstructure of copolymer coating, taking advantage of part solubility of phenol-aniline copolymer in tetrahydrofuran, the bifurcate network structure was observed. The copolymer coating microstructure was summarized, compared with the performance of polyphenol coatings, the reasons of corrosion resistance enhancement with the addition of aniline in electropolymerization reaction was assumed as well.

Hierarchical europium oxalate Eu₂(C₂O₄)₃·10H₂O micro-particles were synthesized through a simple precipitation method at room temperature in present of trisodium citrate. The products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, and photoluminescence. The possible formation mechanism of the hierarchical europium oxalate Eu₂(C₂O₄)₃·10H₂O micro-particles was discussed.

The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973–1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products (ethane and ethylene) compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.

A series of Mo-based catalysts prepared by sol-gel method using citric acid as complexant were successfully applied in the high efficient production of mixed alcohols from bio-syngas, derived from the biomass gasification. The Cu₁Co₁Fe₁Mo₁Zn_0.5⁻6%K catalyst exhibited a higher activity on the space-time yield of mixed alcohols, compared with the other Mo-based catalysts. The carbon conversion significantly increases with rising temperature below 340 °C, but the alcohol selectivity has an opposite trend. The maximum mixed alcohols yield derived from biomass gasification is 494.8 g/(kg_catal·h) with the C2⁺ (C2—C6 higher alcohols) alcohols of 80.4% under the tested conditions. The alcohol distributions are consistent with the Schulz-Flory plots, except methanol. In the alcohols products, the C2⁺ alcohols (higher alcohols) dominate with a weight ratio of 70%–85%. The Mo-based catalysts have been characterized by X-ray diffraction and N₂ adsorption/desorption. The clean bio-fules of mixed alcohols derived from bio-syngas with higher octane values could be used as transportation fuels or petrol additives.

Titanium dioxide sheet photocatalysts composed of interwoven microstrips were successfully synthesized using filter paper as templates. The synthesized samples were characterized by means of Fourier transform infrared spectroscopy, surface area analyzer, thermogravimetric analysis, powder X-ray diffraction, and scanning electron microscopy. The photocatalytic activities of the samples were evaluated by the degradation of methyl orange in an aqueous solution under UV-illumination. The results demonstrated that the paper-like TiO₂ sheets with the optimum proportion of anatase/rutile (10/1) had the highest photoactivity. And the presence of the filter paper fiber can improve the crystallinity, raise the anatase-rutile transformation temperature and contribute to the formation of being paper-like. A detailed formation mechanism for TiO₂ sheets is proposed.

We present a general approach to fabricate metal/TiO₂ core/shell nanorod structures by two-step electrodeposition. Firstly, TiO₂ nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of the nanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO₂ nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.

The influence of Ce doping and the precipitation method on structural properties and the catalytic activity of copper manganese oxides for CO oxidation at ambient temperature have been investigated. The catalysts were characterized by means of the powder X-ray diffraction and N₂ adsorption-desorption, the inductively coupled plasma atomic emission spectrometry, the temperature programmed reduction, diffuse reflectance UV-Vis spectra, and the X-ray photoelectron spectroscopy. It was found that after doping little amount of Ce in copper manganese oxide, CeO₂ phase was highly dispersed and could prevent sintering and aggregating of the catalyst, the size of the catalytic material was decreased, the reducibility was enhanced, the specific surface area was increased and the formation of the active sites for the oxidation of CO was improved significantly. Therefore, the activity of the rare earth promoted catalyst was enhanced remarkably.

Activated carbon fibers (ACFS) with surface area of 1388 m²/g prepared from paper by chemical activation with KOH has been utilized as the adsorbent for the removal of methylene blue from aqueous solution. The experimental data were analyzed by Langmuir and Freundlich models of adsorption. The effects of pH value on the adsorption capacity of ACFS were also investigated. The rates of adsorption were found to conform to the kinetic model of Pseudo-second-order equation with high values of the correlation coefficients (R>0.998). The Langmuir isotherm was found to fit the experimental data better than the Feundlich isotherm over the whole concentration range. Maximum adsorption capacity of 520 mg/g at equilibrium was achieved. It was found that pH played a major role in the adsorption process, higher pH value favored the adsorption of MB.

We describes a controllable synthesis procedure for growing α-Fe₂O₃ and Fe₃O₄ nanowires. High magnetic hematite α-Fe₂O₃ nanowires are successfully grown on Fe_0.5Ni_0.5 alloy substrates via an oxide assisted vapor-solid process. Experimental results also indicate that previous immersion of the substrates in a solution of oxalic acid causes the grown nanowires to convert gradually into magnetite (Fe₃O₄) nanowires. Additionally, the saturated state of Fe₃O₄ nanowires is achieved as the oxalic acid concentration reaches 0.75 mol/L. The average diameter and length of nanowires expands with an increasing operation temperature and the growth density of nanowires accumulates with an increasing gas flux in the vapor-solid process. The growth mechanism of α-Fe₂O₃ and Fe₃O₄ nanowires is also discussed. The results demonstrate that the entire synthesis of nanowires can be completed within 2 h.

Copper indium diselenide nanorod arrays were electrodeposited on tungsten/silicon rigid substrates using porous anodic alumina as growth template. The porous anodic alumina templates were prepared by anodizing aluminum films which were sputtered onto the tungsten/silicon substrates. A selective chemical etching was used to penetrate the barrier layer at the bottom of the alumina channels before electrodeposition, which enables direct electrical and chemical contact with the underside substrate electrode. The as-deposited samples were annealed at 450 °C in vacuum. Scanning electron microscopy revealed that the nanorods were dense and compact with diameter of about 100 nm, length of approximate 1 μm, and the aspect ratio of 10. X-ray diffraction, micro-Raman spectroscopy, and high resolution transmission electron microscopy showed that chalcopyrite polycrystalline structure and high purity CuInSe₂ nanorods were obtained. The grain size was large in the rod axial direction. Energy-dispersive X-ray spectroscopy showed the composition was nearly stoichiometric. The energy band gap of this nanorod arrays was analyzed by fundamental absorption spectrum and was evaluated to be 0.96 eV.

The enthalpies of dissolution of oxymatrine in 0.9%NaCl solution were measured using a RD496-2000 Calvet Microcalorimeter at 309.65 K under atmospheric pressure. The differential enthalpy and molar enthalpy of oxymatrine dissolution in the 0.9%NaCl solution of were determined. The corresponding kinetic equation that described the dissolution process was elucidated. Moreover, the half-life, molar entropy, molar enthaply, and Gibbs free energy of the dissolution process were also obtained.