DFT study of coinage metal-hydrogen associations as hydrogen storage materials stabilized by weakly coordinating anions

Density Functional Theory (DFT) calculations were employed to study a series of coinage metal-hydrogen associations formulated as [M(Η₂)_n][A] (M = Cu^I, Ag^I or Au^I, n = 1–5). The [M(Η₂)_n][A] salts utilize both their anions and cations for H₂ storage. The [M(Η₂)_n]⁺ cations could be stabilized in the solid state by voluminous counter-anions, i.e. the [(H₃B) (BH₂NH₂)₅(NH₂)]^-, [B(CNBH₃)₃]^- and [B₁₂H₁₂]^- anions. The estimated bond dissociation energies (BDEs) of the M···(η²-H₂) bonds are 5–17, 4–11 and 1–26 kcal/mol for the [Cu(Η₂)₄]⁺, [Ag (Η₂)₄]⁺ and [Au (Η₂)₄]⁺ cationic species respectively, while the fifth H₂ molecule is estimated to be very loosely associated to the metal center. Four H₂ molecules could be exploited from the [Cu(Η₂)_n][A] and [Ag (Η₂)_n][A] molecules in addition to the amount of H₂ stored in the anion [A]^-. Among the [M(Η₂)_n][A] salts optimal gravimetric, kinetic and thermodynamic properties and relatively low cost, are predicted for [Cu(Η₂)_n][(H₃B) (BH₂NH₂)₅(NH₂)].     

Markov transition model to dementia with death as a competing event

This study evaluates the effect of death as a competing event to the development of dementia in a longitudinal study of the cognitive status of elderly subjects. A multi-state Markov model with three transient states: intact cognition, mild cognitive impairment (M.C.I.) and global impairment (G.I.) and one absorbing state: dementia is used to model the cognitive panel data; transitions among states depend on four covariates age, education, prior state (intact cognition, or M.C.I., or G.I.) and the presence/absence of an apolipoprotein E-4 allele (APOE4). A Weibull model and a Cox proportional hazards (Cox PH) model are used to fit the survival from death based on age at entry and the APOE4 status. A shared random effect correlates this survival time with the transition model. Simulation studies determine the sensitivity of the maximum likelihood estimates to the violations of the Weibull and Cox PH model assumptions. Results are illustrated with an application to the Nun Study, a longitudinal cohort of 672 participants 75+ years of age at baseline and followed longitudinally with up to ten cognitive assessments per nun.     

An Approximation to the Negative Moments of the Positive Binomial Useful in Life Testing

The purpose of this paper is to obtain the mean and variance of the maximum likelihood estimator of the scale parameter of a Weibull distribution where the sample is censored at a fixed time. It will be shown that these moments are functions of the negative moments of the positive binomial distribution. A simple approximation is obtained for the negative moments of the positive binomial, thus giving an approximate expression for the mean and variance of the estimator.     

Life Tests Under Dependent Competing Causes of Failure

In a life testing situation the failure of an individual, either a living organism or an inanimate object, may be classified into one of k(< 1) mutually exclusive classes, usually causes of failure. One often has dependent causes of failure in actual physical situations, i.e., the theoretical lifetime of an individual failing from one cause may be correlated with the theoretical lifetime of the same individual failing from a different cause. This paper i) discusses some properties of a bivariate Weibull distribution and ii) is concerned with estimating, by the method of maximum likelihood, the unknown parameters of life distributions belonging to two particular parametric families, viz., bivariate normal and bivariate Weibull, when the causes of failure are dependent. An example involving the failure of small electrical appliances is analyzed and compared with an analysis which assumes the causes of failure to be independent.     

Statistical Inference for Power-Law Process With Competing Risks

The focus of this article is on failure history of a repairable system for which the relevant data comprise successive event times for a recurrent phenomenon along with an event-count indicator. We undertake an investigation for analyzing failures from repairable systems that are subject to multiple failure modes. Failure data representing a cluster of recurrent events from a single system are studied under the parametric framework of a power-law process, a model that has found considerable attention in industrial applications. Some interesting and nonstandard asymptotic results ensue in this context that are discussed in detail. Extensive simulation has been carried out that supplements the theoretical findings. An extension to the case where the specific cause of failure may be missing is investigated in detail. The methodology has been implemented on recurrent failure data obtained from a warranty claim database for a fleet of automobiles. Supplementary material for this article is available online.     

The interplay between leadership and organizational culture in the Turkish construction sector

Organizational culture and leadership are purported to be deeply integrated and intertwined within an organization. Although there is a substantial amount of research demonstrating the importance of the interplay of culture and leadership, there exist few empirical examinations of the nature of this link. To examine this link, based on Cameron and Quinn's Organizational Culture Assessment Instrument and Hofstede's Values Survey Module, a questionnaire survey was conducted. The sample consists of 499 managerial personnel out of 107 contracting firms. With the aim of achieving a better understanding of how leadership style is influenced by organizational culture, Multinomial Logistic Regression was used. The findings demonstrate that managers in the contracting companies with different cultural characteristics tend to adopt different leadership styles to lead their employees to succeed in their business. Information contained in this paper will feed into country-specific understanding of leadership and organizational culture within the construction industry.     

基于阴离子交换反应的NiMn-LDH电极电容性能提升研究

采用一步水热法在泡沫镍网上原位生长镍锰基层状双氢氧化物（NiMn-LDH）纳米片阵列电极,并通过氢氧化钾溶液中浸泡的方式提升电极的容量。采用SEM、XRD、TEM和XPS等手段对浸泡前后的电极材料进行表征。结果表明,在浸泡前后NiMn-LDH电极的形貌没有变化,但在电极材料内部发生了明显的CO₃^2-和OH^-的交换反应,降低体积较大的CO₃^2-在LDH层间的分布数量,使层内空间成为OH^-的“蓄水池”,缩短了电荷存储过程中OH^-的迁移距离,因此电容性能有了明显提升。电化学测试结果表明,在5 mA/cm²电流密度下,电极的比电容从18.0 F/g增加至766.6 F/g（1.69 F/cm²）。将该电极与活性炭组装的全固态不对称超级电容器在功率密度为900 W/kg时,可呈现的能量密度为35.9 W·h/kg,并且器件的循环稳定性良好。     

阴离子种类及浓度对RCT催化剂催化湿式氧化处理头孢废水的影响

采用催化湿式氧化法处理头孢类废水,以RCT为催化剂,考察了阴离子对污染物降解效果的影响。结果表明,不加阴离子时,RCT催化剂能有效催化污染物的降解,TOC和TN去除率分别为78.3%和85.9%;投加不同阴离子对反应的影响不同。RCT催化剂可将头孢氨苄废水中的有机N转化为$N_{2}$,少部分以$NO_{3}-N$形式存在;阴离子F^-、Cl^-、Br^-、I-及$S^{2-}_{4}$对TN的降解影响不大,而$N^{-}_{3}$、$P^{3-}_4$、$CO^{2-}_{3}$、$Si^{2-}_{3}$及$B_{4}O^{2-}_{7}$则明显抑制了对TN的去除。投加F^-、Cl^-、Br^-、I-及$NO^{-}_{3}$对TOC的降解有促进作用(I^-> F^-> Cl^-> Br^-> $NO^{-}_{3}$),TOC的降解率提高了3.1~18.6个百分点;而投加$S^{2-}_{4}$、P,$P^{3-}_4$、$CO^{2-}_{3}$、$SiO^{2-}_{3}$及$B_{4}O^{2-}_{7}$对TOC的降解有抑制作用($SiO^{2-}_{3}$> ,$P^{3-}_4$> $CO^{2-}_{3}$> $B_{4}O^{2-}_{7}$> $S^{2-}_{4}$),TOC的降解率降低了2.0~46.9个百分点。研究Cl-浓度对RCT催化剂降解效果的影响,当Cl-为0.1 mol·L-1时,对TOC的去除有抑制作用,而较高的Cl-浓度(≥0.3 mol·L-1)对TOC的去除却有促进作用,投加Cl-对TN的去除有促进作用,但随着Cl-浓度的增加[(0.1~0.8) mol·L-1],TN的去除率变化不明显(约为88%)。     

Effect of backwashing on perchlorate removal in fixed bed biofilm reactors

The influence of backwashing on biological perchlorate reduction was evaluated in two laboratory scale fixed bed biofilm reactors using 1- or 3-mm glass beads as support media. Influent perchlorate concentrations were 50 microg/L and acetate was added as the electron donor at a concentration of 2 mg C/L. Perchlorate removal was evaluated at various influent dissolved oxygen (DO) concentrations. Complete perchlorate removal was achieved with an influent DO concentration of 1mg/L resulting in bulk phase DO concentrations below the detection limit of 0.01 mg/L. The influence of increasing influent DO concentrations for 12 h periods was evaluated before and after individual backwash events. Partial perchlorate removal was achieved with an influent DO concentration of 3.5 mg/L before a strong backwash (bulk phase DO concentrations of approximately 0.2mg/L), while no perchlorate removal was observed after the strong backwash at the same influent DO level (bulk phase DO concentrations of approximately 0.8 mg/L). The immediate effect of backwashing depended on influent DO concentrations. With influent DO concentrations of 1 mg/L, strong backwashing resulted in a brief (<12 h) increase of effluent perchlorate concentrations up to 20 microg/L; more pronounced effects were observed with influent DO concentrations of 3mg/L. Daily weak backwashing had a small and, over time, decreasing negative influence on perchlorate reduction, while daily strong backwashing ultimately resulted in the breakdown of perchlorate removal with influent DO concentrations of 3 mg/L.