稀释气对离子电流影响的试验研究与机理分析

针对稀释气体影响离子电流前锋区特征峰的研究比较缺乏,以甲烷/空气/稀释气体为对象,通过在定容燃烧弹内布置离子电流测量电极,获得了稀释气种类N2/CO2/Ar和0%、5%、10%、15%几种不同稀释比条件下离子电流的特征峰值,结合CHEMKIN化学反应动力学数值模拟结果,分析了主导离子电流前锋区信号生成的带电组分的数密度、敏感性系数及其生成路径。试验结果表明:相同的稀释比下,CO2稀释对离子电流信号的抑制作用最大;在不同的稀释气体种类下,离子电流前锋区峰值均在过量空气系数λ为0.95时达到最大。数值计算结果表明,对离子电流前锋区信号贡献最大的组分是H3O+和电子e,链分支反应R38、链终止反应R52和离子化初始反应R326对这两种组分浓度的影响较大。在过量空气系数λ为0.95时,O和CH数密度都较大且反应区温度最高,导致化学离子化程度最大,离子电流值前锋区峰值也达到最大值。该结论为研究稀释气体对燃料燃烧的离子电流信号影响和火焰锋面电学特性提供了一定的机理支撑。

Cation effects in electrocatalytic reduction reactions:Recent advances

Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N_(2)/NO_(x),organics,and O_(2))into high-value-added chemicals or fuels.The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions.However,bottle-necks are encountered,making it challenging to further improve performance through catalyst development alone.Recently,cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions.This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions.First,we introduce the mechanisms underlying cation effects.We then provide a comprehensive overview of their application in electroreduction reactions.Characterization techniques and theoretical calcula-tion methods for studying cation effects are also discussed.Finally,we address remaining challeng-es and future perspectives in this field.We hope that this review offers fundamental insights and design guidance for utilizing cation effects,thereby advancing their development.

Mechanistic Investigation on the Reaction of O- with CH3CN Using Density Functional Theory

The potential energy profile of the reaction between the atomic oxygen radical anion and acetonitrile has been mapped at the G3MP2B3 level of theory. Geometries of the reactants, products, intermediate complexes, and transition states involved in this reaction have been optimized at the （U）B3LYP/6-31＋G（d,p） level, and then their accurate relative energies have been improved using the G3MP2B3 method. The potential energy profile is confirmed via intrinsic reaction coordinate calculations of transition states. Four possible production channels are examined respectively, as H＋ transfer, H-atom transfer, H2＋ transfer, and bi- molecular nucleophilic substitution （SN2） reaction pathways. Based on present calculations, the H2＋ transfer reaction is major among these four channels, which agrees with previous experimental conclusions.

C-S Activation of CS2 by Nb＋ in Gas Phase

The reaction of Nb＋ with CS2, producing cationic transition-metal sulfide and CS, was taken as a representative example to elucidate the overall mechanism of reactions of second- row early transition metal ions with CS2. The reactions in both triplet and quintet state were studied by using the UB3LYP density functional method with the Stuttgart pseudo potentials and corresponding basis sets for Nb＋ and the standard 6-311＋G（2d） basis sets for C and S. The geometries for reactants, the transition states, and the products were completely optimized. All the transition states were verified by vibrational analysis and intrinsic reaction coordinate calculations. The results show that the reaction mechanism between niobium ion and CS2 is an insertion-elimination mechanism. Intersystem crossing may occur in the reaction Nb＋ with CS2 and a minimum energy crossing point was found.

Enhancement of leaching of cobalt and lithium from spent lithium-ion batteries by mechanochemical process

A mechanochemical method with SiO_(2)as the grinding aid was used to enhance the leaching efficiencies of Co and Li from spent lithium batteries(LIBs).Experiment results show that the optimal leaching efficiencies of 94.91%for Co and 97.22%for Li were obtained under the parameters of SiO_(2)/LiCoO_(2)mass ratio of 1:1,grinding speed of 500 r/min and grinding time of 30 min in citric acid.Characterization results indicate that the surficial properties of LiCoO_(2)were changed after mechanochemical grinding treatment due to the newly generated surfaces on LiCoO_(2).Meanwhile,the incompletely coordinated atomic structure and defective lattice structure lead to the activation of LiCoO_(2).The reduction effect of carbon black on Co^(3+)under the action of mechanical forces increases its leaching efficiencies in the citric acid solution.The proposed process was found efficiently to recover Co and Li from LiCoO_(2).

Nanotechnology:fundamental research to product development

The concept of an integrated "lab on a chip" has long been a goal for the micro-electro-mechanical-systems(MEMS) community.This would entail the integration of not only the sampling and analysis of various functions,but also the ability to transmit this information off the chip to a central repository.This paper describes the initial steps in the fabrication of a "lab on a chip" which would continually analyze blood sampled via microneedles using techniques such as nano plasmonics,specifically,concentrations of glucose.The analysis could then be transmitted off the chip using digital signal processing.This paper describes the analysis and optimization of the microneedle shape and size and the fabrication of the resulting needles in silicon using deep reactive ion etching(DRIE).The paper also describes the opportunities for fabrication of such needles in alternative materials and describes the issues that still have to be overcome before such an integrated device is realized.