Studies on polyethylene glycol/polyethersulfone composite membranes for FCC gasoline desulphurization by pervaporation

A polyethylene glycol (PEG)/polyethersulfone (PES) composite membrane that can be applied on a commercial (or scale up) plant for fluid catalytic cracking (FCC) gasoline desulphurization was prepared through pre-wetting combined with double-layer coating methodology. Preparation methodology, morphologies characterization and performance test for the composite membranes were conducted. The results indicated that the pre-wetting method effectively confined the intrusion of PEG solution to porous PES support layer in coating process. The composite membrane had a clear-cut boundary surface between the dense active layer and the porous support layer, which was examined by scanning electron microscope (SEM). Pervaporation (PV) experiments indicated that the membrane, with the crosslinking agent amount of 17% and solids content in active layer solution of 16%, had a stable performance for FCC desulphurization. The sulphur enrichment factor came to 3.63, and the total permeation flux was 3.37 kg/m² h. It was found that the PV performance of the composite membrane changed slightly when the thickness of active layer varied from 4.25 μm to 33.26 μm.     

理论研究氧原子与富勒烯C60(Ih)的相互作用

运用密度泛函理论(DFT)方法,研究了异构体C60O[6,6]与C60O[5,6]之间的重排反应机理。结果显示: 它们之间的反应路径是经过一个过渡态没有中间体的一步反应。C60O[6,6] 转化成C60O[5,6]的反应能垒是42.7 kcal*mol-1,在反方向,C60O[5,6]转化成C60O[6,6]的反应能垒是47.3 kcal*mol-1,同时,扫描出氧原子在富勒烯C60(Ih)表面的势能面（PEC）,以详细显示异构体C60O[6,6]与C60O[5,6]之间的重排反应机理。     

将SVRT模型应用到单原子多原子反应F+CH2 D2→CH2 D/CHD2 +DF/HF中

The semirigid vibrating rotor target（SVRT）model is applied for the reaction F+CH2D2→CH2D/CHD2+DF/HF. The time-dependent wave packet approach is also used in the calculation. Reaction probabilities,crosssections,and rate constants are calculated for the title reaction from the ground state of the reagent on the modified J1（MJ1）potential energy surface（PES）for both channels. Numerical calculation shows the oscillatory structures in the energy dependence of the calculated reaction probability. Those structures are generally associated with broad dynamical resonances. They are smooth in the energy dependence of integral cross-sections due to summation over partial waves. The calculated rate constants are in good agreement with the experimental measurement.     

基于CASSCF参考函数的块相关耦合簇方法对烷烃中单键解离势能面研究

用以完全活化空间自洽场(CASSCF)波函数为参考波函数的块相关耦合簇(BCCC)方法(简称CAS-BCCC)研究了烷烃(甲烷和乙烷)中的单键解离过程的势能面(PES). 与其它理论方法比较的结果表明, 该方法可以对所研究的整个解离势能面给出定量准确的描述.     

Computational study on mechanisms and pathways of the atmospheric NH2 + IO reaction

ABSTRACT

The potential-energy surfaces of the amino radical (NH₂) with IO reaction have been studied at the CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) level. Two kinds of pathways are revealed, namely H-abstraction and addition/elimination. Rice–Ramsperger–Kassel–Marcus theory and transition state theory are employed to calculate the overall and individual rate constants over a wide range of temperatures and pressures. It is predicted that, at atmospheric pressure with N2 as bath gas, the formation of P1 (HI?+?HNO) is the dominant pathways at 200–700?K, while the direct H-abstraction leading to P3 (³NH?+?HOI) takes over the reaction at a temperature above 700?K. At the high-pressure limit, IM1 [IONH₂] formed by collisional stabilisation is dominant at 200–700?K; the direct H-abstraction resulting in P3 (³NH?+?HOI) plays an important role at higher temperatures. However, the total rate constants are independence on the pressure; however, the individual rate constants are sensitive to pressure. The atmospheric lifetime of NH₂ in IO is around one week. TD-DFT computations imply that IM1 [IONH₂], IM1A [IONH₂′], IM2 [IN(H₂)O], IM3 [OINH₂], IM4 [HOINH], tra-IM5 [tra-HON(H)I] and cis-IM5 [cis-HON(H)I] will photolyze under the sunlight.     

A quantum chemical study on •Cl-initiated atmospheric degradation of CH2BrO2•

The singlet and triplet potential energy surfaces for the CH₂BrO₂??+??Cl reaction have been researched theoretically. All of the probable reaction routes were investigated by using B3LYP and G3(MP2) models. Addition/elimination and S_N2 displacement exist on the singlet potential energy surfaces (PES), and the foremost approach process of CH₂BrO₂??+??Cl is generating IM1 (CH₂BrOOCl) with no barrier, followed by the O-O bond breaking accompanied by an H-migrate resulting in the most abundant product P1 (CHBrO?+?HClO). One direct H-abstraction and three S_N2 displacement reaction pathways exist on the triplet PES, and direct H-abstraction is the foremost pathway. RRKM-TST theory was employed to predict product distribution of the CH₂BrO₂??+??Cl reaction. At atmospheric pressure, the production of P1 (CHBrO?+?HClO) by addition/elimination dominants the reaction at T?≤?800?K, while the direct H-abstraction takes over the reaction at T?>?800?K. The total rate constants are insensitive to pressure, and the branching rate constants are just the opposite. The lifetime of CH₂BrO₂? in the presence of ?Cl was predicted to 3.2?d. Moreover, time-dependent density functional theory (TDDFT) calculations suggest that IM1 (CH₂BrOOCl), IM2 (CH₂BrOClO) and IM3 (CH₂(OBr)OCl) will photolyze under the sunlight.     

Hamiltonian of a Slightly Asymmetric Molecules with a Three Fold Internal Rotor and Its Applications to Optically Pumped FIR Lasers: Theoretical Aspects

In this paper, a Model of the Hamiltonian function is reviewed for the slightly asymmetric class of molecules, which is the most successful so far, according to our present knowledge. This model does not have the redundancy problem suffered by previous models. The observed frequencies are calculated to within experimental accuracy. In our subsequent papers we will show the application of this model for the prediction and quantum number assignments of optically pumped far infrared lasers and thereby increasing the possibility of new lines in the region of the spectrum which severely lacks enough monochromatic sources. We will also show that this model is capable of calculating even MMW transitions for the second excited state of methanol. All the previous models consider transitions up to the first excited torsional state.     

Low energy structures of gold nanoclusters in the size range 3–38 atoms

Using a combination of first principles calculations and empirical potentials we have undertaken a systematic study of the low energy structures of gold nanoclusters containing from 3 to 38 atoms. A Lennard-Jones and many-body potential have been used in the empirical calculations, while the first principles calculations employ an atomic orbital, density functional technique. For the smaller clusters (n=3–5) the potential energy surface has been mapped at the ab initio level and for larger clusters an empirical potential was first used to identify low energy candidates which were then optimised with full ab initio calculations. At the DFT-LDA level, planar structures persist up to six atoms and are considerably more stable than the cage structures by more than 0.1 eV/atom. The difference in ab initio energy between the most stable planar and cage structures for seven atoms is only 0.04 eV/atom. For larger clusters there are generally a number of minima in the potential energy surface lying very close in energy. Furthermore our calculations do not predict ordered structures for the magic numbers n=13 and 38. They do predict the ordered tetrahedral structure for n=20. The results of the calculations show that gold nanoclusters in this size range are mainly disordered and will likely exist in a range of structures at room temperature.     

Potential energy surfaces for low-lying electronic states of SO_2

The sulfur dioxide molecule (SO2) is an important atmospheric pollutant primarily from sulfur-containing materials combustion processes[1]. Because of its im- portance in atmospheric photochemistry, as well as in atmospheric dynamics, this molecule has been the subject of much experimental[2―10] and theoreti- cal[11―19] photochemical study for many years. They provide a wealth of information about the SO2 spec- trum, predissociation mechanism, vibration including vibration-rotation interact…     

Theoretical study on the mechanism of the (3)CH(2) + NO(2) reaction

The complex doublet potential energy surface of the CH(2)NO(2) system is investigated at the B3LYP/6-31G(d,p) and QCISD(T)/6-311G(d,p) (single-point) levels to explore the possible reaction mechanism of the triplet CH(2) radical with NO(2). Forty minimum isomers and 92 transition states are located. For the most relevant reaction pathways, the high-level QCISD(T)/6-311 + G(2df,2p) calculations are performed at the B3LYP/6-31G(d,p) geometries to accurately determine the energetics. It is found that the top attack of the (3)CH(2) radical at the N-atom of NO(2) first forms the branched open-chain H(2)CNO(2) a with no barrier followed by ring closure to give the three-membered ring isomer cC(H(2))ON-O b that will almost barrierlessly dissociate to product P(1) H(2)CO + NO. The lesser followed competitive channel is the 1,3-H-shift of a to isomer HCN(O)OH c, which will take subsequent cis-trans conversion and dissociation to P(2) OH + HCNO. The direct O-extrusion of a to product P(3) (3)O + H(2)CNO is even much less feasible. Because the intermediates and transition states involved in the above three channels are all lower than the reactants in energy, the title reaction is expected to be rapid, as is consistent with the measured large rate constant at room temperature. Formation of the other very low-lying dissociation products such as NH(2) + CO(2), OH + HNCO and H(2)O + NCO seems unlikely due to kinetic hindrance. Moreover, the (3)CH(2) attack at the end-O of NO(2) is a barrier-consumed process, and thus may only be of significance at very high temperatures. The reaction of the singlet CH(2) with NO(2) is also briefly discussed. Our calculated results may assist in future laboratory identification of the products of the title reaction.