Characterizing the Role of Iodine Doping in Improving Photovoltaic Performance of Dye‐Sensitized Hierarchically Structured ZnO Solar Cells

We report two novel types of hierarchically structured iodine‐doped ZnO (I? ZnO)‐based dye‐sensitized solar cells (DSCs) using indoline D205 and the ruthenium complex N719 as sensitizers. It was found that iodine doping boosts the efficiencies of D205 I? ZnO and N719 I? ZnO DSCs with an enhancement of 20.3 and 17.9 %, respectively, compared to the undoped versions. Transient absorption spectra demonstrated that iodine doping impels an increase in the decay time of I? ZnO, favoring enhanced exciton life. Mott–Schottky analysis results indicated a negative shift of the flat‐band potential (V_fb) of ZnO, caused by iodine doping, and this shift correlated with the enhancement of the open circuit voltage (V_oc). To reveal the effect of iodine doping on the effective separation of e^?‐h⁺ pairs which is responsible for cell efficiency, direct visualization of light‐induced changes in the surface potential between I? ZnO particles and dye molecules were traced by Kelvin probe force microscopy. We found that potential changes of iodine‐doped ZnO films by irradiation were above one hundred millivolts and thus significantly greater. In order to correlate enhanced cell performance with iodine doping, electrochemical impedance spectroscopy, incident‐photon‐current efficiency, and cyclic voltammetry investigations on I? ZnO cells were carried out. The results revealed several favorable features of I? ZnO cells, that is, longer electron lifetime, lower charge‐transfer resistance, stronger peak current, and extended visible light harvest, all of which serve to promote cell performance.     

一个含呋喃环顺磁性碳硼烷衍生物的合成及其生成机理

半夹芯16e化合物CpCoS₂C₂B₁₀H₁₀（Cp：cyclopentadienyl）（1）与2-呋喃炔酮在物质的量比为1：1.5时反应分离得到1个顺磁性化合物CpCoS₂C₂B₁₀H₉（C₁₂H₁₀O₂）（2）。在化合物2的合成过程中,一分子1中的Cp环与另一分子1中的B（3）/B（6）位连接;同时,该Cp环与1个2-呋喃炔酮分子发生Diels-Alder反应,生成1个双环[2.2.1]-2-庚烯基结构单元。此外,呋喃炔酮分子中的末端炔基碳原子与原料1中的1个硫原子相连,从而使得产物2中的钴中心离子是个17e中心。化合物2用红外、核磁、元素分析,质谱和单晶X-射线衍射分析等方法进行了表征。晶体属三斜晶系,空间群P1,晶胞参数：a=0.96657（11）nm,b=1.54423（15）nm,c=1.75650（18）nm,α=114.0800（10）°,β=105.433（2）°,γ=98.6390（10）°。     

The Special Issue Dedicated to the Memory of Professor Wei-Shan Zhou(周维善)

This special issue is dedicated to the memory of thelate Professor Wei-Shan Zhou at Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences.     

A Highly Selective Colorimetric Sensor for Cu2+ Based on Phenolic Group Biscarbonyl Hydrazone

A novel copper selective sensor 2 based on hydrazide and salicylaldehyde has been designed and prepared. Sensor 2 behaves a single selectivity and sensitivity in the recognition for Cu²⁺ over other metal ions such as Fe³⁺, Hg²⁺, Ag⁺, Ca²⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ni²⁺, Co²⁺, Cr³⁺ and Mg²⁺ in DMSO. The distinct color change and the rapid changement of fluorescence emission provide naked‐eyes detection for Cu²⁺. The UV‐vis data indicate that 1:2 stoichiometry complex is formed by sensor 2 and Cu²⁺. The association constant K_s was 3.51×10⁴ mol^?1·L. The detection limitation of Cu²⁺ with the sensor 2 was 2.2×10^?7 mol·L^?1. The sensing of Cu²⁺ by this sensor was found to be reversible, with the Cu²⁺‐induced color being lost upon addition of EDTA.     

ZnFe2O4/Ag/TiO2复合材料的制备及其光催化性能

以硝酸银、钛酸四丁酯、无水氯化锌、六水氯化铁为原料,采用溶胶-凝胶法与溶剂热相结合的方法制备了ZnFe₂O₄/Ag/TiO₂复合材料,通过扫描电子显微镜、能谱分析仪、X射线粉末衍射仪、X射线光电子能谱仪、振动样品磁强计、紫外可见分光光度计对样品进行表征及测试。结果表明： ZnFe₂O₄/Ag/TiO₂-10具有最佳的光催化效果,在紫外和可见光下对染料的降解率都能达到90%以上,具有优异的紫外可见光光催化活性。ZnFe₂O₄/Ag/TiO₂具有独特的磁性,能在外部磁场作用下进行回收利用,这使其在实际应用中成为可能。通过磁分离技术重复回收利用5次后仍然保持优良的光催化性能,说明ZnFe₂O₄/Ag/TiO₂-10具有优异的磁性及较高的光催化循环稳定性。     

钴(Ⅲ)催化CpCoS2C2B10H10分子内B(3)/B(6)位和Cp配体偶联

半夹芯16e化合物CpCoS₂C₂B₁₀H₁₀(Cp：cyclopentadienyl) (1)与HC≡CCO₂Me在2-甲基二硫代丙酸存在下反应生成化合物{(C₅H₄CoS₂C₂B₉H₉)(CH=CHCO₂Me)(Me₂c=CS₂H)} (2)和(Me₂c=CS₂H)₃Co (3)。在化合物2中, 原料化合物1中的一个S-Co键断裂, 该S原子与一分子HC≡CCO₂Me末端炔基碳原子连接。Co原子与2-甲基二硫代丙酸的S原子连接成键, 2-甲基二硫代丙酸分子中的SH基团与Co原子通过配位键相连;同时, Cp环的一个碳原子与碳硼烷笼体的B(3)/B(6)位相连, 该B(3)/B(6)位的氢原子迁移到炔烃HC≡CCO₂Me的内部炔基碳原子上形成反式烯键。3个2-甲基二硫代丙酸分子中的3个S原子分别与1中的Co原子通过共价键连接, 3个SH基团与Co原子通过配位键相连, 从而形成化合物3。化合物2和3分别用红外、核磁、元素分析、质谱和单晶X-射线衍射分析等方法进行了表征。     

不饱和半夹芯式16e化合物Cp*Ir(S2C2B10H10)与邻、间位取代苯基叠氮的反应性

考虑取代基的位置和电子效应对反应体系的影响, 本文系统地研究了16e化合物Cp^*Ir(S₂C₂B₁₀H₁₀) (1)与邻、间位取代苯基叠氮的反应。研究结果表明：与邻、间位取代苯基叠氮反应均生成苯环邻位碳发生C-H 活化形成C-S 键的金属配合物。这些配合物通过核磁(¹H、¹¹B、¹³C)、红外、质谱、元素分析和单晶结构解析进行了全面地表征。在光照反应结果的基础上, 提出了形成这类产物的自由基机理。