Synthesis of new di-anchoring organic sensitizer based on quinoxaline acceptor for dye-sensitized solar cells

New quinoxaline-based organic sensitizer bearing di-anchoring group for dye-sensitized solar cells (DSSCs) was synthesized from diethyl 4,5-diaminophthaltate, in which was prepared under mild condition by using Takehito’s method. The synthesized sensitizer was compared with mono-anchoring sensitizer through absorption spectra, emission spectra, J-V curve, and IPCE spectra, indicating the di-anchoring group leads to a noticeable improvement of J_sc value owing to more efficient intramolecular charge transfer and channel number increment.     

敏化型电致发光器件原理与技术

近年来,高性能荧光有机电致发光器件(FOLEDs)的开发受到了广泛关注。由于荧光材料仅能利用25%的单重态激子辐射发光,FOLEDs的外量子效率(EQE)理论极限为5%。通过能量转移,充分利用主体分子的单重态与三重态激子敏化荧光客体发光,可以提高激子利用率。目前敏化型FOLEDs(SFOLEDs)的最高EQE已达26.1%。本文详细介绍了SFOLEDs的敏化原理和机制,并根据敏化机制的不同,系统地总结了热活化延迟荧光敏化、激基复合物敏化、三重态湮灭敏化和局域电荷转移杂化激发态(HLCT)敏化等各类SFOLEDs的材料与器件结构特点及其研究进展。最后本综述对该类器件的研究前景进行了展望,期待吸引更多专业的研究人员的研究兴趣,进而推动该领域的发展。     

Fabrication of PbS nanocrystal-sensitized ultrafine TiO2 nanotubes for efficient and unusual broadband-light-driven hydrogen production

It is highly desired to maximize the use of solar light by developing broadband-light-responsive H₂ production system in the field of photocatalysis. Herein, a novel PbS/(Pt–TiO₂) nanocomposite with efficient and unusual broadband-light-driven H₂ production feature is constructed by using infrared-bandgap PbS nanocrystals as sensitizer of Pt-loaded ultrafine anatase TiO₂ nanotubes (Pt–TiO₂). After optimizing the component ratio, the resultant PbS/(Pt–TiO₂) nanocomposite delivers a H₂ production activity of 813 and 186 μmol h^?1 under ultraviolet (UV)-visible (Vis)-near-infrared (NIR) and Vis-NIR light irradiation, respectively. Moreover, an apparent quantum yield of 38.6%, 26.2%, 2.43%, 3.21%, 2.17%, 0.36%, 0.11% and 0.01% can be attained from the PbS/(Pt–TiO₂) nanocomposite illuminated at 350, 420, 550, 700, 760, 850, 950 and 1064 nm monochromatic light, respectively. The intimate interfacial contacts in the PbS nanocrystals decorated ultrafine TiO₂ nanotubes, which serve as the support and electron acceptor of PbS nanocrystals, can effectively promote the photoexcited hot electrons transferring from PbS nanocrystals to TiO₂ nanotubes before the thermalization losses, and thus causing the efficient Vis-NIR-light-responsive H₂ production activity of the PbS/(Pt–TiO₂) nanocomposite. These results provide an intriguing application of infrared-bandgap materials to exploit the low-energy photons of the solar light for constructing efficient and unusual broadband-responsive H₂ production system.     

Geometry,Electronic Structure,and Related Properties of Dye Sensitizer： 3,4-bis[1- （carboxymethyl）-3-indolyl]- 1 H-pyrrole-2,5-dione

The geometry, electronic structure, polarizability and hyperpolarizability of dye sensitizer 3,4-bis[1-（carboxymethyl）-3-indolyl]-1H-pyrrole-2,5-dione （BIMCOOH） were studied using density functional theory （DFT） with hybrid functional B3LYP, and the electronic absorption spectra were investigated using semi-empirical quantum chemical method ZINDO-1 and time-dependent DFT （TDDFT）. The results of natural bond orbital suggest that the natural charges of the dione, indole, and acetic groups are about 0.15e, -0.29e, and 0.44e, respectively. The calculated isotropic polarizability, polarizability anisotropy invariant and hyperpolarizability are 305.4, 188.3, and 1155.4 a.u., respectively. The electronic absorption spectral features in visible and near-UV region were assigned to the π→π^＊ transition due to the qualitative agreement between the experiment and the TDDFT calculations, and the transitions of the excited states 9-11 related to photoinduced intramolecular charge transfer processes. The analysis of electronic structure and UV-Vis absorption indicates that the indole groups primarily contributed sensitization of photo-to-currency conversion processes, and the interracial electron transfer between semiconductor TiO2 electrode and dye sensitizer BIMCOOH are electron injection processes from excited states of the dyes to the semiconductor conduction band.     

照相明胶与化学增感剂相互作用的XPS研究

本文采用Ｘ射线光电子能谱技术研究了两种照相明胶与化学增感剂相互作用的机理．当两种照相明胶样品在ＨＡｕＣｌ４溶液中反应５ｍｉｎ后，明胶中的蛋氨酸、蛋氨酸亚砜均被氧化为蛋氨酸砜．与此同时，明胶吸附的大部分Ａｕ３＋被还原为Ａｕ＋，并且Ａｕ＋以络合形态存在于明胶之中．根据与ＡｕＣｌ３反应之后明胶中Ａｕ３＋与Ａｕ＋的比例，法国明胶的还原性略高于包头明胶．添加到明胶中的Ｎａ２Ｓ２Ｏ３能将明胶大分子所含的蛋氨酸亚砜全部还原为蛋氨酸．Ｓ２Ｏ３２－、蛋氨酸和蛋氨酸砜可以稳定共存于明胶体系之中，外加的Ｓ２Ｏ３２－的还原性高于明胶中蛋氨酸、蛋氨酸亚砜的还原性．添加Ｎａ２Ｓ２Ｏ３后的两种照相明胶均可以将其溶胀吸附的Ａｕ３＋全部还原为胶态金．此时，参与氧化还原反应的主要基团是Ｓ２Ｏ３２－而非明胶中的蛋氨酸残基．由于Ｎａ２Ｓ２Ｏ３的添加，照相明胶对ＡｕＣｌ３的还原能力增强     

Geometry, Electronic Structure, and Related Properties of Dye Sensitizer:3,4-bis[1-(carboxymethyl)-3-indolyl]-1H-pyrrole-2,5-dione

运用密度泛函理论中的杂化泛函B3LYP研究了太阳能电池染料敏化剂3,4-二-[1-(羧甲基)-3-吲哚]-1H-吡咯-2,5-二酮(BIMCOOH)的几何结构、电子结构、极化率和超极化率，并用半经验量子化学方法ZINDO-l和含时密度泛函理论(TDDFT)研究了电子吸收谱．自然键轨道方法的研究结果表明，布居于二酮、吲哚和乙酸基团的自然电荷分别为-0.15e、-0.29e、0.44e．计算的各向同性极化率、极化率各向异性不变量和平均超极化率分别是305.4、188.3、1155.4 a.u.．基于TDDFT的计算结果和实验结果的定性符合指认了在可见和近紫外区的吸收属于∏→∏*跃迁，并且TDDFT的计算结果显示，第9～11个激发态的跃迁与光诱导分子内电荷转移过程有关．对电子结构和紫外-可见吸收谱的分析表明，吲哚基团对光电转换过程的敏化起主要作用，发生于染料敏化剂BIMCOOH和TiO2电极界面之间的电荷转移是由染料分子激发态向半导体导带的电子注入过程．     

Density Functional Theory Study on Organic Dye Sensitizers Containing Bis-dimethylfluorenyl Amino Benzofuran

运用密度泛函理论和含时密度泛函理论研究了两种含二-二甲基芴氨基苯并呋喃基团的有机染料敏化剂的几何结构、电子结构、极化率和超极化率以及紫外可见谱. 基于理论计算和实验结果的一致性指认了电子吸收谱的特征. 可见区的吸收带都与光诱导电荷转移过程有关，二甲基芴氨基苯并呋喃基团是在光电转换敏化中起主要作用的基团. 通过对两种染料敏化剂的比较，分析了亚乙烯基对几何结构、电子结构和光谱特性影响.     

Synthesis,structural, electrochemical,and photophysical properties of 4,2′‐thiopyrylogens – a novel class of sensitizers for photoinduced electron transfer reactions

The first three examples of the thioanalog of the 4,2′‐pyrylogen ring system are reported. The influence of the sulfur atom on the structural, electrochemical, and photophysical behavior of this ring system is discussed. In addition, these 4,2′‐thiopyrylogens are compared to their previously reported 4,4′‐isomers and their 4,4′‐ and 4,2′‐oxygen analogs. Copyright © 2010 John Wiley & Sons, Ltd.     

Development of an information-intensive structure–activity relationship model and its application to human respiratory chemical sensitizers

Structure–activity relationship (SAR) models are recognized as powerful tools to predict the toxicologic potential of new or untested chemicals and also provide insight into possible mechanisms of toxicity. Models have been based on physicochemical attributes and structural features of chemicals. We describe herein the development of a new SAR modeling algorithm called cat-SAR that is capable of analyzing and predicting chemical activity from divergent biological response data. The cat-SAR program develops chemical fragment-based SAR models from categorical biological response data (e.g. toxicologically active and inactive compounds). The database selected for model development was a published set of chemicals documented to cause respiratory hypersensitivity in humans. Two models were generated that differed only in that one model included explicate hydrogen containing fragments. The predictive abilities of the models were tested using leave-one-out cross-validation tests. One model had a sensitivity of 0.94 and specificity of 0.87 yielding an overall correct prediction of 91%. The second model had a sensitivity of 0.89, specificity of 0.95 and overall correct prediction of 92%. The demonstrated predictive capabilities of the cat-SAR approach, together with its modeling flexibility and design transparency, suggest the potential for its widespread applicability to toxicity prediction and for deriving mechanistic insight into toxicologic effects.     

Spectral Characteristics of White Organic Light-emitting Diodes Based on Novel Phosphorescent Sensitizer

采用新型贵金属铱的配合物bis(1,2-dipheny1-1H-benzoimida-zole)iridium (acetylacetonate)作为磷光敏化剂,与荧光染料4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-en-yl)-4H-pyran共同掺杂到聚合物主体材料poly(N-vinylcarbazole)中，以N,N'-diphenyl-N,N'-bis(1-naphthyl) (1,1'-biphenyl)-4,4'-diami-ne作为蓝光发光层，制备了白色有机电致发光器件. 通过对掺杂体系的紫外-可见吸收光谱、光致发光光谱以及电致发光光谱的表征，分析了该磷光敏化体系的能量转移机制. 结果表明，在该聚合物磷光荧光双掺杂体系中，由于磷光与荧光材料之间的不完全的F?rster能量传递过程，导致电致发光光谱中同时存在磷光材料三线态到基态与荧光材料单线态到基态的辐射衰减发光. 该掺杂体系成功实现了白光发射，随着偏置电压的升高，器件的CIE色坐标有微小的红移，但都非常接近等能白光点，器件表现出了很好的色纯度.