LO-phonon effect on the exciton binding energy in polar rectangular quantum wires

Longitudinal optical phonon effect on Wannier excitons in polar rectangular quantum wires is studied by a variational approach. The binding energy is calculated and the numerical results for several II-VI and III-V compound semiconductor rectangular quantum wires are given. The results show that the phonon effect reduces the binding energy and cannot be neglected. The phonon contribution to the binding energy is sensitive to the size of the rectangular quantum wire section, and increases with decreasing section area. The results for the GaAs rectangular quantum wires coincide with the experimental results. The calculated binding energy and the phonon effect in II-VI QWWs are both stronger than those in III-V compound systems, and the results for ZnSe QWW are qualitatively in agreement with the experiments.     

一类非线性Burgers方程组的基于Hopf-Cole变换的直接间断Galerkin有限元方法

<正>1引言Burgers方程可以作为描述许多物理现象的数学模型,如交通流、激波、扰流问题和连续的随机过程.它还可以用于检验数值方法的效率.由于其具有较广的实用范围,一些学者对其近似解进行了较多的研究.如Adomian分解方法、混合有限差分和边界元方法、样条有限元方法、精确显式有限差分方法、Douglas有限差分格式,直接变分方法和变分迭代方法被用于Burgers方程近似解的研究~([1-13]).Hopf-Cole变换~([14,15])是研究Burgers方程较好的分析工具,利用它可以获得Burgers方程一些精确解.近年来,人们意识到该变换也是一个很好的数值工具并利用其得到了一     

模板-聚合法Pd/Al2O3催化剂制备及其蒽醌加氢性能研究

以丙烯酸铵为模板剂,由油柱成型法制备了系列球形Al2O3载体,采用XRD、BET等分析测试手段对其晶体结构、比表面积、孔容和孔径分布进行了表征,结果表明,600℃焙烧的球形γ-Al2O3载体具有介孔结构,并且比表面较不使用模板剂的样品有大幅度增加。焙烧温度升至960℃得到δ-Al2O3,介孔结构消失,但由于结构记忆效应,载体的大表面特性得以保持。以δ-Al2O3为载体制备Pd/Al2O3催化剂,采用氢-氧滴定(HOT)方法测定发现,比表面的增加显著提高了Pd金属的分散度,从而大幅度提高了催化剂的蒽醌加氢活性,氢化效率最高可达10.5 g.L-1。     

磷化镍催化剂的制备机理及其加氢脱氮性能

采用热重-质谱联用技术研究了次磷酸盐在氮气中的热分解过程,探讨了次磷酸盐热分解法制备磷化镍的反应机理:次磷酸镍中的Ni²⁺能够"催化"H₂PO₂^-低温发生歧化反应生成PH₃,继而还原Ni²⁺得到Ni₂P。制备了不同负载量的Ni₂P/SiO₂催化剂,用X射线衍射(XRD)、低温N₂吸附-脱附、高分辨透射电镜(HRTEM)等分析技术对催化剂结构进行表征。结果表明,Ni₂P活性组分在SiO₂载体上具有良好的分散性,颗粒粒径为5～8 nm。以喹啉为加氢脱氮模型化合物,在高压微型固定床反应器上对催化剂活性进行评价,在反应温度为360℃、氢气压力为2.0 MPa、液时空速为2.0 h^-1、氢油体积比为500:1时,Ni₂P(20%)/SiO₂催化剂的加氢脱氮率为41.5%。     

The photoisomerization of 11‐cis‐retinal protonated schiff base in gas phase: Insight from spin‐flip density functional theory

This extensive theoretical study employed the spin‐flip density functional theory (SFDFT) method to investigate the photoisomerization of 11‐cis‐retinal protonated Schiff base (PSB11) and its minimal model tZt‐penta‐3,5‐dieniminium cation (PSB3). Our calculated results indicate that SFDFT can perform very well in describing the ground‐ and excited‐state geometries of PSB3 and PSB11. We located the conical intersection (CI) point and constructed the photoisomerization reaction path of PSB3 and PSB11 by using the SFDFT method. To further verify the SFDFT results, we computed the energy profiles along the constructed linearly interpolated internal coordinate (LIIC) pathways by using high‐level theoretical methods, such as the EOM‐CCSD, CR‐EOM‐CCSD(T), CASPT2, NEVPT2, and XMCQDPT2 methods. The SFDFT method predicts that the photoisomerization of PSB3 is barrierless, in accordance with previous complete‐active‐space self‐consistent‐field (CASSCF) results. However, an energy barrier is predicted along the LIIC pathways of PSB11. This finding is different from previous CASSCF results and may indicate that the photoisomerization of PSB11 in gas phase is similar to that in solution. However, the higher spin contamination of the SFDFT method in the vicinity of the CI point caused the located CI geometry to deviate from that of the real CI. In addition, the LIIC pathways are only approximations to the minimum energy path (MEP). Thus, further experimental and theoretical studies are needed to verify the existence of an energy barrier along the photoisomerization reaction path of PSB11 in gas phase. © 2013 Wiley Periodicals, Inc.     

Ni-Mo/Al_2O_3催化剂上硫转移反应的研究

制备了以γ-Al2O3为载体的Ni-Mo催化剂,并用于FCC汽油的加氢硫转移反应。对Ni-Mo/Al2O3催化剂上的硫转移反应机理进行了研究,考察了不同反应条件对硫转移反应的影响。实验结果表明,硫醇与烯烃的反应在催化剂表面的加氢活性位上进行,小分子的硫醇发生加氢脱硫,生成吸附态H2S,吸附态的H2S与烯烃反应,生成大分子硫醇和硫醚;另外小分子硫醇还可直接与烯烃发生反应,生成硫醚。提高反应温度、压力、氢油比或降低空速,均可提高催化剂的硫转移反应活性,轻质硫转化率得到明显提高,且单烯选择性还能维持在98%左右。     

Solvent extraction of U(VI) by trioctylphosphine oxide using a room-temperature ionic liquid

The unique physical and chemical properties of room-temperature ionic liquids(RTILs) have recently received increasing attention as solvent alternatives for possible application in the field of nuclear industry, particularly in liquid-liquid separations of radioactive nuclides. We investigated solvent extraction of U(VI) from aqueous solutions into a commonly used ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([C4mim][NTf2]) using trioctylphosphine oxide(TOPO) as an extractant. The effects of contact time, TOPO concentration, acidity, and nitrate ions on the U(VI) extraction are discussed in detail. The extraction mechanism was proposed based on slope analysis and UV-Vis measurement. The results clearly show that TOPO/[C4mim][NTf2] provides a highly efficient extraction of U(VI) from aqueous solution under near-neutral conditions. When the TOPO concentration was 10 mmol/L, the extraction of 1 mmol/L U(VI) was almost complete( 97%). Both the extraction efficiency and distribution coefficient were much larger than in conventional organic solvents such as dichloromethane. Slope analysis confirmed that three TOPO molecules in [C4mim][NTf2] bound with one U(VI) ion and one nitrate ion was also involved in the complexation and formed the final extracted species of [UO2(NO3)(TOPO)3]+. Such a complex suggests that extraction occurs by a cation-exchange mode, which was subsequently evidenced by the fact that the concentration of C4mim+ in the aqueous phase increased linearly with the extraction percent of U(VI) recorded by UV-Vis measurement.     

限域NiCo合金纳米颗粒高效催化生物质衍生物水相加氢脱氧

将储量丰富的生物质及其衍生物转化为具有高附加值的燃料和化学品被认为是一种有前景的绿色途径,可以极大地减少人们对传统化石资源的依赖.作为木质纤维素热解的直接产物和生物油升级的模型化合物,香草醛可以通过加氢脱氧(HDO)过程选择性地转化为2-甲氧基-4-甲基苯酚(MMP).MMP是一种有价值的化学品,常用于香料和药物等重要中间体的合成.在过去十年里,大量的金属催化剂被用来催化香草醛HDO转化为MMP.其中,贵金属(Pt,Pd,Ru和Au)虽然活性高,但是其储量低、价格昂贵,不利于工业化应用;而非贵金属(Fe,Co,Ni和Cu)的催化活性普遍较低,需要苛刻的反应条件来提高转化效率和选择性.此外,这类HDO反应大都在有机溶剂中进行,容易造成环境污染.因此,开发高效、稳定的非贵金属催化剂用于水相HDO反应是一个巨大的挑战.一般来说,合金纳米颗粒(NPs)具有强烈的协同效应,能产生良好的配位结构和电子环境,从而显著提升催化活性和选择性.基于此,本文首次采用了一种简单可控的合成方法来制备三聚氰胺海绵负载的氮掺杂碳纳米管(N-CNTs)限域的Ni-Co合金NPs(NiCo@N-CNTs/CMF)催化剂.该催化剂具有优异的HDO性能,在2 MPa H2,120oC反应6 h条件下,能在水相中将生物质衍生的香草醛高效转化为MMP,转化率和选择性均达到100％.相比于单金属的Ni@N-CNTs/CMF和Co@N-CNTs/CMF催化剂,香草醛转化率和MMP选择性都有大幅度的提高.而且,在温和的反应条件下,该催化剂对香草醛衍生物和其他芳香醛类化合物同样表现出优异的HDO性能,拥有100％的转化率以及较高的MMP选择性(91.5％～100％).XPS结果表明,Ni-Co形成合金后发生了电子结构的偏移,即Co原子可以从邻近的Ni原子处得到电子,提高Co电子云密度,从而促进对香草醛中C=O键的吸附.DFT计算结果表明,相比于单金属的Ni和Co,Ni-Co合金化后能显著提高对C=O键的选择性吸附和活化.同时,H2解离后形成的活性H*物种在Ni-Co合金NPs表面更容易脱附并参与催化反应.因此,Ni-Co@N-CNTs/CMF催化剂优异的HDO性能主要是由于Ni-Co合金NPs的协同作用大大促进了其对C=O键的选择性吸附和活化,以及活化氢物种的脱附.本文为设计和制备高效的非贵金属催化剂应用于水相的HDO反应提供了一个新策略.     

基于光楔阵列产生光学涡旋阵列的研究

在研究光楔衍射法产生单涡旋的基础上,基于长条形光楔阵列,提出了利用光束阵列衍射产生涡旋阵列的方法.该方法要求光束阵列在平行于光楔边缘方向上的光束间距等于光束直径的整数倍.利用超精密机床采用一体化加工法加工了光楔阵列元件,验证了该方法的可行性.利用空间光调制器快速灵活调整光束阵列的优点,搭建了借助空间光调制器加载达曼光栅衍射产生所需光束阵列的实验光学系统.针对光束阵列与光楔阵列的匹配问题,研究了达曼光栅掩模图基本单元对光束阵列的调控,获得了可调结构的光束阵列.实验产生了拓扑荷一致的光学涡旋阵列,与仿真结果相一致,证明所提方法的有效性.     

液态丙烯腈低聚物修复聚丙烯腈基碳纤维微孔缺陷

提出一种全新的缺陷修复的方法,即将聚丙烯腈基(PAN)碳纤维T300在液态丙烯腈低聚物(LAN)中浸渍后,再进行预氧化和碳化热处理,可以将T300的拉伸强度提高25%.应用二维小角X射线散射(SAXS)法可以计算出LAN修复缺陷前后T300微孔缺陷的长度(L)、横截面尺寸(lp)、取向角(Beq)、相对体积(Vrel)的变化,结果表明碳纤维的拉伸性能越好,微孔的长度、取向角、相对体积含量越小.T300拉伸性能的提高是由于缺陷修复的结果.应用BET比表面积法、扫描电子显微镜(SEM)表征LAN修复缺陷前后T300的比表面积以及表面形貌的变化,结果表明,T300在LAN中浸渍并经过预氧化和碳化热处理,比表面积变小,表面缺陷明显减少.进一步验证LAN对碳纤维中的微孔缺陷具有修复作用.应用X射线光电子能谱(XPS)法表征LAN修复前后T300表面化学成分的变化,结果表明,LAN修复后含氧官能团(C―OH,C=O,HO―C=O)显著增加,有利于增强碳纤维与树脂基体之间的相互作用,从而提高碳纤维的力学性能.