硫/碳复合材料在锂硫电池正极中的应用

锂硫电池由于具有1675 mAh·g-1的高理论比容量和2600 Wh·kg-1的高理论能量密度,被看做是下一代最有前景的二次电池能源储存系统之一.但是,多硫化物的穿梭效应、活性物质导电性差以及充放电过程中的体积膨胀效应等问题阻碍了其进一步商业化.为了解决这些问题,不同的材料被引入和硫进行复合.在所有材料的选择中,碳材料由于具有高的表面积、优异的导电性、化学稳定性和低成本等优势在锂硫电池正极中得到了广泛应用.本文总结了几种不同的碳材料在硫/碳复合正极中的发展历程,讨论了碳材料的结构、孔径大小以及表面功能化对锂硫电池电化学性能的影响,并对其前景以及发展趋势作了预测.     

基于数字全息的热透镜效应测量

提出一种数字全息定量测量半导体激光二极管侧面泵浦Nd∶YAG晶体热透镜效应的方法。CCD采集Nd∶YAG晶体在不同泵浦电流下的数字全息图,通过数值重建得到热透镜效应引起的相位分布及其变化过程。再由相位分布计算得到对应的热透镜焦距。实验结果表明,利用数字全息技术可以准确和有效测量热透镜效应及热透镜焦距。     

曲面相机阵列多分辨成像方法

针对现有成像系统因数据冗余而无法兼顾大视场、高分辨、高效性的问题,结合人眼视网膜变分辨成像和并列式复眼成像原理,设计一种多分辨率成像的复合仿生成像系统.该成像系统按照球面和平面兼顾的曲面布局方式,利用11个相机镜头构建相机阵列,组成了四个等级分辨率的子眼拍摄模块.通过物距100 m的远景实验和物距10 m的近景实验发现,该系统在实现高分辨成像的同时,获得总视场达150.8°×37.8°.多分辨率成像实验结果表明,该系统获取的图像的分辨率从中心视场到边缘视场逐渐降低,并且相较于中心清晰全视场成像,四级分辨率成像的拼接图像数据量减少了17.2倍的数据冗余.     

全无机钙钛矿量子点的合成、性质及发光二极管应用进展

近年来,全无机铯铅卤素钙钛矿(CsPb X 3,X=Cl,Br,I)量子点由于其色纯度高、具有可调谐的发射波长(410~760 nm)、窄的半峰宽(12~42 nm)和较高的荧光量子产率(最高可达95%以上)以及可全溶液处理等优势而受到人们的高度关注,在显示和照明领域有着较为广阔的应用前景。本文首先介绍了近年来发展起来的全无机钙钛矿量子点的液相合成方法,如高温热注射法、一步反应法、阴离子交换法和过饱和重结晶法等;其次介绍了全无机钙钛矿量子点的形貌、尺寸和晶型调控及材料组分、反应温度和杂质离子对其发光性能的影响,进而总结了无铅全无机钙钛矿量子点的研究进展;然后介绍了全无机钙钛矿量子点在发光二极管方面的应用进展;最后概述了全无机钙钛矿量子点在未来发展中存在的挑战和机遇。     

表面喷砂对有机玻璃沿面闪络性能影响

绝缘子表面粗糙处理是提升其沿面闪络性能的重要途径,表面粗糙化处理方式不当,极易带来表面结构不均匀,难以获得稳定耐压性能的绝缘材料。为提升绝缘子表面粗糙处理的均匀性,本文利用表面喷砂技术对圆柱形有机玻璃(PMMA)绝缘子进行了粗糙化处理研究,以球形二氧化硅(SiO2)颗粒为工作介质,研究了不同喷砂粒径、氢氟酸后处理等因素对绝缘材料表面形貌和组分的影响,并利用短脉冲高压测试平台对喷砂处理前后有机玻璃绝缘子样品进行了真空沿面闪络性能测试。研究结果表明,喷砂处理在有机玻璃表面形成了较为均匀的凹坑,HF酸能够有效去除表面残留的SiO2颗粒,具有表面喷砂粗糙结构的绝缘子沿面闪络电压得到了稳定提升,相较于未处理的绝缘子闪络电压提升了约80%。     

第32届江苏省化学竞赛选拔赛有机化学试题解析*

利用有机化学基础知识和理论对第32届江苏省化学竞赛选拔赛试题有机化学部分进行详细解析,为指导老师和参赛学生提供参考。     

Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene-hydride of Cp2M(L)H [Cp = η5-C5H5; M = Nb,V; L = CO,P (OMe)3]: A DFT study

The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)- or (E)-type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp₂M(L)H [Cp = η⁵-C₅H₅; M = Nb, V; L = CO, P (OMe)₃] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z-isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG^#). Then the Z-pro converts to E-pro , while for L = P (OMe)₃, the exclusive product is the E-isomer. For different metal centers, the reaction mechanisms of the Cp₂M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z-pro to E-pro is low and the relative free energies of Z-pro and E-pro are almost equal, both Z-pro and E-pro can be obtained. While for the Cp₂V(CO)H + DMAD reaction, only the Z-pro can be obtained under mild conditions, E-pro can be obtained only at high temperatures. For the Cp₂M(CO)H+DMAD(M=V and Nb) reactions, the formation of E-isomer products proceeds via two five-membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction.     

浸渍吸附法制备Ag-SiO2纳米复合抗菌材料的条件优化

运用浸渍吸附法制备了纳米级单分散Ag-SiO2无机复合抗菌材料,结合响应曲面方法,考察了Ag+浓度、反应时间和氨水添加量等因素对材料抗菌率的影响,考虑到材料制备成本,变色控制等多方面因素,选取了最优制备条件,实验结果表明:Ag+浓度为5.9×10-4 mol·L-1,氨水添加量为4.1 mL,反应时间为5.2 h时,材料有最佳的经济效益和抗菌性能,抗菌率达到91.7;.通过TEM、XRD、ICP和BET方法对材料的结构进行表征,结果表明:载体SiO2微球为无定形态;Ag-SiO2抗菌材料微球具有良好的分散性和稳定性,粒径尺寸均匀;Ag+成功负载于SiO2微球表面,负载量为8.10 mg·kg-1.     

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E=S or Se; R=nPr,iPr or iBu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu₃₀H₁₈{S₂P(OnPr)₂}₁₂] ( 1_H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1_H reveals an unprecedented central Cu₁₂ hollow icosahedron. Six faces of this icosahedron are capped by Cu₃ triangles, the whole Cu₃₀ core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S₆ symmetry. The locations of the 18 hydrides in 1_H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ₃-H, interstitial μ₄-H (seesaw) and μ₅-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the ¹H NMR spectrum of 1_H are in line with their coordination environment in the solid state, retaining the S₆ symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu₃₀H₁₈{Se₂P(OR)₂}₁₂] ( 2_H : R=iPr 3_H : R=iBu) were synthesized from their sulfur relative 1_H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1_H – 3_H . In addition, the reaction of 1_H with [Pd(PPh₃)₂Cl₂] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu₁₄H₂{S₂P(OnPr)₂}₆(C≡CR)₆] ( 4 : R=Ph; 5 : R = C₆H₄F).     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.