Cyclopentadienyl rhodium(III) complexes as catalysts for the insertion of phenyldiazoacetate into E−H bonds

Rhodium(III) complexes catalyze the insertion of carbenoids generated from diazo compounds into E?H bonds (E = B, Si, N, but not C), although less efficiently than classical rhodium(II) carboxylates, despite formally higher oxidation state of the metal.     

Phosphoric-Acid Retention in High-Temperature Proton-Exchange Membranes

Great efforts have been conducted to develop high temperature proton exchange membrane fuel cell (HT-PEMFC) due to its features of enhanced electrocatalyst reactivity, simplified hydrothermal management system and high CO tolerance of catalysts, and remarkable progress has been achieved. However, the easy leaching of phosphoric acid (PA) from the membranes during operation limits its commercial scale-up in complicated environments. This concept here mainly focuses on the recent developments for mitigation of PA loss in PEMs. The probable mechanisms of PA loss are proposed. The approaches to improve PA retention for example via introduction of phosphonic acid by covalent bond, using ion-pairs interaction and siphoning effect, and blending with inorganic nanoparticles are described in detail. Among these strategies, the siphoning effect from the intrinsic microporous PEMs is the most efficient and enables the cell to operate flexibly within a broad temperature range. Therefore, this concept may provide new ideas for the scientists to retain PA, to improve the cell performance and expand the potential applications of PA doped PEMs at elevated humidity and wide temperature range.     

Enhanced dielectric and nonohmic properties of SrTiO3-modified CaCu3Ti4O12 ceramics

Dielectric and nonohmic properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics can be modified by addition of SrTiO₃ (STO) in different molar proportions which were fabricated by a modified sol-gel method. XRD results indicated that all modified ceramics showed mixed phase consisting of both CCTO and STO. SEM images and grain size distribution probability also presented the change of microstructure with the addition of STO. The dielectric loss of the CCTO/0.4STO ceramics sintered at 1000 °C can be lower than 0.02 in a wide frequency (1 kHz–10 kHz), especially at 1 kHz, the dielectric loss of this sample is as low as 0.012. Furthermore, excellent nonlinear I–V electrical characteristic (high breakdown voltage to 54.15 kV/cm for CCTO/0.4STO sintered at 1000 °C) was observed as well. All the results indicated that the addition of STO does improve the dielectric properties and nonohmic characteristics of CCTO ceramics dramatically.     

明代生命损失型地震的时空分布特征及成因分析

利用史料记录建立了明代生命损失型地震的数据库，构建生命损失型地震等级序列、10 a尺度上生命损失型地震的频次序列和县次序列，再现明代生命损失型地震的时空分布特征，探讨了生命损失型地震发生及导致人口死亡的时空差异原因。结果表明：（1）从明初到明末，生命损失型地震等级强度有逐渐扩大的趋势。（2）明代前期处于生命损失型地震发生较少的稳定时期；明代中后期处于生命损失型地震发生较多的波动时期。明代生命损失型地震发生频次存在明显的周期性变化特征。（3）生命损失型地震在明代大部分区域皆有分布。灾害重心随时间变化发生移动，由西南到中部再到华北、华东。（4）明代地震频繁的原因除地球本身因素外，太阳活动通过影响气候变化，进而间接影响地壳活动。气候寒冷与干旱和地震有较好的对应关系。明代后期生命损失型地震导致死亡人数大量增加，与明代经济发展，人口密度逐渐增长有关；不同地区生命损失型地震导致的死亡人数不同，且死亡人数与地震频发地区是否处于板块之间的活动构造带和人口分布密度有关。     

水流损失和热补偿共同作用对增强型地热系统(EGS)产能影响的研究

基于青海共和盆地-3705m地热田实测数据,结合流固耦合传热理论并运用Comsol软件,建立了离散型裂隙岩体流体传热模型。考虑水流损失和热补偿共同作用,模拟得到了开采过程中上、下岩层(盖层和垫层)为绝热不渗透、传热不渗透、渗透传热时,储层(上、下岩层和压裂层)温度场的变化特征,分析了产出流量、水流损失、产出温度、产热速率的变化规律。研究结果表明:采热过程中产出流量始终小于注入流量;产出流量增幅速率先增大后减小,最后趋于稳定,前3a产出流量增幅超过总增幅量的3/4;忽略水流损失,将高估产热速率,采热初期甚至达到考虑水流损失时产热速率的3倍以上;考虑水流损失,产热速率呈先快速上升再趋于稳定后逐渐下降的趋势,最优开采时间为3a^11a;研究上、下岩层对产出温度的影响,仅考虑传热,采热寿命延长5.43%,同时考虑渗流传热时,采热寿命延长2.71%;采热前9a,水流损失占主导作用,即流入上、下岩层水流损失对产热速率的影响高于热补偿效应,开采10a后,热补偿效应占主导作用;同时考虑水流损失和热补偿效应得到的产热速率变化规律与实际工程更为符合,建议选择低渗透能力的上、下岩层延长增强型地热系统(EGS)运行时间。     

Analytical formulas for complex permittivity of periodic composites. Estimation of gain and loss enhancement in active and passive composites

ABSTRACT

The asymptotic homogenization method is applied to complex dielectric periodic composites. An equivalence to coupled dielectric problems with real coefficients is shown. This is similar to a piezoelectric problem: an out-plane mechanical displacement and an in-plane electric potential establishing a correspondence principle. Closed-form formulas for the complex dielectric effective tensor in the case of a square array of circular inclusions embedded in a matrix are given. These formulas are written in terms of a real and symmetric matrix which facilitates the implementation of the computational scheme. We also get similar formulas for multilayered complex dielectric composites. The real closed-form formulas are advantageous for estimating gain and loss enhancement properties of active and passive composites in certain volume fraction intervals. Numerical computations are performed and the results are compared with other approaches showing the usefulness of the obtained formulas. This may be of interest in the context of metamaterials.     

小孔流速实验中的排水时间和流量系数的研究

本文以水作为理想流体,考虑到水头损失和孔口缩流效应,对小孔流速实验涉及的容器排水问题进行了系统的理论和实验研究.从理论上推导得出了圆柱形容器排水时间的解析解,分析了排水时间和自由液面速度、流量系数之间的规律,提出了排水时间的等效性.实验上,加工了底部开有不同小孔的大型圆柱形容器,测量了容器排水时间随液面高度的变化关系,借助实验结果计算了流量系数值,验证了容器排水时间的等效性关系,实验结果与理论计算符合较好.     

Mechanism of Insertion Reactions between Silylenoid H2SiLiF and GeH3R (R =F,OH, NH2): a Theoretical Study

Theoretical investigations on the insertion reaction mechanisms of three- membered-ring silylenoid H2 Si Li F with GeH 3R(R = F, OH, NH2) have been systematically carried out by combined density functional theory(DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3 LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex(Q), one transition state(TS), and one intermediate(IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with Ge H3 R proceed in a concerted manner, forming H2RSi-Ge H3 and Li F. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 k J/mol, and the reaction energies for the three reactions are –127.05, –116.91, and –103.31 k J/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH 3-F GeH 3-OH GeH 3-NH2. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation.