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1.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
2.
Tuning the Basicity of Cyano‐Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interactions
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Dr. Guokai Cui Fengtao Zhang Xiuyuan Zhou Prof. Haoran Li Prof. Jianji Wang Prof. Congmin Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5632-5639
A new approach has been developed to improve SO2 sorption by cyano‐containing ionic liquids (ILs) through tuning the basicity of ILs and cyano–sulfur interaction. Several kinds of cyano‐containing ILs with different basicity were designed, prepared, and used for SO2 capture. The interaction between these cyano‐containing ILs and SO2 was investigated by FTIR and NMR methods. Spectroscopic investigations and quantum chemical calculations showed that dramatic effects on SO2 capacity originate from the basicity of the ILs and enhanced cyano–sulfur interaction. Furthermore, the captured SO2 was easy to release by heating or bubbling N2 through the ILs. This efficient and reversible process, achieved by tuning the basicity of ILs, is an excellent alternative to current technologies for SO2 capture. 相似文献
3.
运用群论及原子分子反应静力学方法,推导了XY(H,Li,Na)分子基态的电子态及相应的离解极限.并采用密度泛函方法(B3LYP)和二次组态相互作用方法(QCISD)优化计算了XY(H,Li,Na)分子基态的平衡结构、振动频率和离解能.使用QCISD/6-311++G(3df,3pd)方法,对XY(H,Li,Na)分子基态进行了单点能扫描计算,采用最小二乘法拟合Murrell-Sorbie函数得到了相应的势能函数和与该基态相对应的光谱常数(Be,αe,ωe和ωexe),计算结果与实验数据符合得相当好. 相似文献
4.
采用甚高频等离子体增强化学气相沉积技术制备了系列微晶硅薄膜太阳电池,指出了气体总流量和背反射电极的类型对电池性能参数的影响.电池的I-V测试结果表明:随反应气体总流量的增加,对应电池的短路电流密度、开路电压和填充因子都有很大程度的提高,结果使得电池的光电转换效率得以提高.另外,ZnO/Ag/Al背反射电极能明显提高电池的短路电流密度,进而也提高了电池的光电转换效率.对气体总流量和背反射电极类型影响电池效率的原因进行了分析.
关键词:
微晶硅薄膜太阳电池
气体流量
ZnO/Ag/Al背反射电极 相似文献
5.
6.
Geng Sheng WANG 《数学学报(英文版)》2005,21(5):1005-1014
This work is concerned with Pontryagin's maximum principle of optimal control problems governed by some non-well-posed semilinear heat equations. A type of approach to the non-well-posed optimal control problem is given. 相似文献
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8.
光突发交换的交换控制策略和光缓存配置 总被引:4,自引:2,他引:2
光突发交换是面向下一代互联网的光交换模式.讨论了异步光突发交换系统的交换控制策略以及相应光缓存的优化配置策略.除了传统预约模式的交换策略,还研究了非预约和改进型预约模式,它们的性能评估由计算机仿真给出.结果表明:在条件相当情况下,改进型预约模式具有最低的丢包率.同时光缓存的配置对上述几类交换控制策略的性能都有很大影响,仿真结果指出:光缓存的粒度对系统性能具有重要影响,所讨论的几类交换模式都存在最佳时延粒度,研究结果对光交换矩阵的设计有指导意义. 相似文献
9.
Settling of a large solid particle in bioconvection flow caused by gyrotactic microorganisms is investigated. The particle is released from the top of the bioconvection chamber; its settling pattern depends on whether it is released in the centre of the bioconvection plume or at its periphery. The Chimera method is utilized; a subgrid is generated around a moving particle. The method suggested by Liu and Wang (Comput. Fluid 2004; 33 :223–255) is further developed to account for the presence of a moving boundary in the streamfunction‐vorticity formulation using the finite‐difference method. A number of cases for different release positions of the particle are computed. It is demonstrated that bioconvection can either accelerate or decelerate settling of the particle depending on the initial position of the particle relative to the plume centre. It is also shown that the particle impacts bioconvection plume by changing its shape and location in the chamber. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
10.
Two quantities ηrel and are applied to study the nonideal acetone–water association mixture. An all-atom acetone model and a TIP5P water model have been adopted for molecular dynamics simulation. We study the transport properties of the system comparing the 's of strong hydrogen bond and weak contact based on transport properties, MD simulations together with NMR experimental data and find good agreement of concentration dependence, which exhibits the cooperation effect. 相似文献