Mechanisms for formation,chlorination, dechlorination and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) constitute a group of persistent organic pollutants that form almost inexorably in all thermal and combustion operations. This review focuses on mechanisms that govern their formation, chlorination, dechlorination and destruction. As a consequence of their extreme toxicity and propensity to bioaccumulate, PCDD/Fs have been subjected to much scientific research, designed to understand mechanisms and conditions that govern their emission rates and congener distribution (fingerprints). Consensus of opinions in the literature points to heterogeneous pathways contributing substantially more in the total yield of PCDD/Fs in combustion systems than the gas phase pathway. However, in our view, a great complexity of both homogeneous and heterogeneous routes and uncertainties in many thermochemical and rate parameters enable no conclusive statement about the contribution of each route. Chlorination patterns of precursors appear to play a major role in final congener profiles of PCDD/F emissions. According to the most recent theoretical studies, these congener profiles seem consistent with thermodynamic stabilities of dioxins and furans produced in thermal processes, however, further theoretical investigations at more accurate levels are needed to clarify this matter further. Theoretical studies along with experimental findings reveal that the PCDD/PCDF ratio remains very sensitive to the operating conditions, with pyrolytic conditions favouring the formation of PCDFs. A number of reaction mechanisms has been proposed to answer many of the most intriguing questions about the formation of PCDD/Fs. These mechanisms include models of gaseous and heterogeneous reactions, often inferred from theoretical quantum chemical calculations studies, which incorporate steps responsible for formation, chlorination, dechlorination and destruction of dioxins and furans. The review identifies gaps in our present understanding of the reaction mechanisms and suggests that further progress in the field needs to be facilitated by development of reliable mechanistic models for (i) catalytic pathways, (ii) chlorination/dechlorination reactions including the Deacon reaction and the direct transfer of chlorine from solid surfaces into the aromatic moieties, and (iii) formation of PCDD/Fs from precursors other than chlorophenols, especially pesticides.     

浅谈大学英语教学中的文化导入

语言和文化的关系是密不可分的 ,学习一种语言 ,就必须学习这种语言所代表的文化。大学英语教学除了培养学生掌握英语语言知识外 ,还必须培养他们的跨文化交际能力     

Aromatic Borozene

Based on our comprehensive theoretical investigation and known experimental results for small boron clusters, we predict the existence of a novel aromatic inorganic molecule, B₁₂H₆. This molecule, which we refer to as borozene, has remarkably similar properties to the well-known benzene. Borozene is planar, possesses a large first excitation energy, D _3h symmetry, and more importantly is aromatic. Furthermore, the calculated anisotropy of the magnetic susceptibility of borozene is three times larger in absolute value than for benzene. Finally, we show that borozene molecules may be fused together to give larger aromatic compounds with even larger anisotropic susceptibilities.     

1-乙基-3-甲基咪唑四氟硼酸盐离子液体结构性质的模拟计算

离子液体以其独特的性质广受关注,被称为绿色设计者溶剂,人们对其潜在的应用价值做了大量的研究.实验采用HyperChem软件构建了1-乙基-3-甲基咪唑四氟硼酸盐([EMIM][BF4])离子液体分子结构的3D模型,并用PM3法进行预优化,然后应用Gaussian 03w程序分别在RHF/6.31G(d)和BLYP/6-31G(d)计算水平上进行量子化学计算,并经振动频率和强度分析得到理论红外谱图.结果表明,[EMIM][BF4]离子液体的阴阳离子存在着氢键等弱相互作用.     

Ab initio insights into the visible luminescent properties of ZnO

The luminescence spectrum of ZnO exhibits, besides a UV band-edge recombination line, a broad visible band around 2.2-2.4 eV whose origin has not been satisfactorily established. Recently, analysis of the luminescence of nanostructured materials with high surface-to-volume ratios has led some authors to suggest that the band could be related to surface states. This work presents a novel ab initio study of the most relevant ZnO surfaces and their intrinsic point defects. It reveals the existence of intragap surface states 0.5 eV above the valence band maximum. If additional bulk defect levels are considered, several bulk-to-surface transitions are compatible with the observed visible luminescence.     

单相电压骤降特征量的求导检测算法

动态电压恢复器(dynamic voltage restorer,DVR)是改善电压质量的一种有效工具。在电网电压骤降的情况下,能否快速而准确地检测出电网电压骤降的特征量将直接影响到DVR的补偿效果。文章在研究现有的电压骤降特征量检测方法的基础上,提出一种适用于单相电压骤降的ab求导检测算法,利用求导来代替ab变换方法中的相位延迟算法,并且考虑了发生电压骤降过程中可能伴随的谐波的影响。仿真分析结果表明,该算法检测精度较高,实时性好,满足DVR检测的需要。     

First Principles Analysis of the Electrocatalytic Oxidation of Methanol and Carbon Monoxide

The strong drive to commercialize fuel cells for portable as well as transportation power sources has led to the tremendous growth in fundamental research aimed at elucidating the catalytic paths and kinetics that govern the electrode performance of proton exchange membrane (PEM) fuel cells. Advances in theory over the past decade coupled with the exponential increases in computational speed and memory have enabled theory to become an invaluable partner in elucidating the surface chemistry that controls different catalytic systems. Despite the significant advances in modeling vapor-phase catalytic systems, the widespread use of first principle theoretical calculations in the analysis of electrocatalytic systems has been rather limited due to the complex electrochemical environment. Herein, we describe the development and application of a first-principles-based approach termed the double reference method that can be used to simulate chemistry at an electrified interface. The simulations mimic the half-cell analysis that is currently used to evaluate electrochemical systems experimentally where the potential is set via an external potentiostat. We use this approach to simulate the potential dependence of elementary reaction energies and activation barriers for different electrocatalytic reactions important for the anode of the direct methanol fuel cell. More specifically we examine the potential-dependence for the activation of water and the oxidation of methanol and CO over model Pt and Pt alloy surfaces. The insights from these model systems are subsequently used to test alternative compositions for the development of improved catalytic materials for the anode of the direct methanol fuel cell.     

Quantum chemical studies on molecular conformations,energetic and intramolecular hydrogen bonding in ground and electronic excited state of (thioxosilyl) ethyleneselenol

In this work, a conformational analysis of (thioxosilyl) ethyleneselenol was performed using several computational methods, including density-functional theory (DFT) (B3LYP), MP2 and G2MP2. Harmonic vibrational frequencies were estimated at the same levels to confirm the nature of the stationary points found and also to account for the zero point vibrational energy correction. MES-1 and TES-1 conformers exhibit hydrogen bonding. This feature, although is not the dominant factor in the stability of conformers, appears to be of foremost importance to define the geometry of the molecule. Two intramolecular hydrogen bonds established between the polar groups were identified by the structural geometric parameters. These involved the thiol and selenol functional groups and were identified and characterized by the frequency shift in their stretching vibration modes. Furthermore, the excited-state properties of intramolecular hydrogen bonding have been investigated theoretically using the time-dependent DFT method. The influence of the solvent on the stability order of conformers and the strength of intramolecular hydrogen bonding was considered using the PCM (polarizable continuum model), SCI-PCM (self consistent isodensity-polarizable continuum model) and IEF-PCM (integral equation formalism-polarizable continuum model) methods. The “atoms in molecules” theory of Bader was used to analyze critical points and to study the nature of hydrogen bond in these systems. Natural bond orbital (NBO) analysis was also performed for better understanding the nature of intramolecular interactions. The calculated highest occupiedmolecular orbital and lowest unoccupied molecular orbital energies show that charge transfer occur within the molecule. Further verification of the obtained transition state structures was implemented via intrinsic reaction coordinate analysis. Calculations of the ¹H NMR chemical shift at the GIAO/B3LYP/6–311++G** level of theory are also presented.     

The interpretation of X-ray photoelectron spectra of pyrolized S-containing carbonaceous materials

Theoretical models and ab initio Hartree-Fock wavefunctions have been used to investigate the S(2p) core level binding energies (BE), of pyrolized S-containing, carbonaceous materials. Comparison between experimental and calculated data for thiophene permits the accuracy of the present approach to be established. A systematic study of different situations demonstrates that, in these materials, non-oxidized S atoms can show peaks at very high BE relative to the C(1s) peak at 285.0 eV. This study confirms that the peak at 164.1 eV corresponds to ‘thiophenic’ S atoms. On the other hand, it shows that the peaks at higher BE could correspond to S atoms replacing C atoms in three-coordinated structures of graphene layers, in agreement with the arguments suggested in the experimental works. The energetic similarity between the two peaks at very high BE makes it difficult to differentiate between them, although the results of the present study seem to suggest that the peak at experimental BE ≈ 166 eV could correspond to S atoms coordinated to two C and one H atoms at the edge of graphene layers, while the peak at ≈ 169 eV would correspond to S atoms replacing C atoms in inner positions of the graphene layers, and it is bonded to three C atoms.