染料敏化纳米晶体TiO2太阳能电池的对电极结构

通过对染料敏化纳米晶体TiO₂太阳能电池的对电极的结构进行改进,设计了一种可大容量储存电解质和补充电解质的新型对电极结构.当染料敏化纳米晶体TiO₂太阳能电池因液态电解质挥发泄漏而失效时,可以对其进行液态电解质的及时补充,从而使失效的染料敏化纳米晶体TiO₂太阳能电池重新恢复工作.该新型对电极结构为解决染料敏化纳米晶体TiO₂太阳能电池由于液态电解质泄漏导致的寿命降低问题提供了一种新的解决方法.     

有机染料敏化网状二氧化钛纳米纤维微孔膜太阳能电池研究

利用静电纺丝技术, 在TiO₂纳米粒子上电纺一层网状TiO₂纳米纤维微孔膜作为光散射层, 并在TiO₂纳米粒子中掺杂少量MgO以抑制电子和空穴的复合, 得到TiO₂纳米纤维/纳米粒子复合光阳极用于染料敏化太阳能电池. 将这种光阳极分别与有机三苯胺染料SD2, SD3或钌染料N719及鹅脱氧胆酸(CDCA)共敏化时, 在AM 1.5 (100 mW/cm²)的模拟太阳光照射下, 染料敏化太阳能电池的光电转换效率达到6.35%～8.85%. 同时, 使用半固态电解质可以达到液态电解质90%的光电转换效率.     

基于有机二硫化物氧化还原电对的非碘系染料敏化太阳能电池

相比较于硅太阳能电池而言, 染料敏化太阳能电池具有成本低廉、制备简单的特点. 在目前研究中, 普遍采用碘离子作为氧化还原电对, 然而碘元素本身具有腐蚀性, 长期使用会腐蚀对电极从而影响器件寿命, 而且此类电解液在可见光区内有很强的吸收, 也不利于光能向电能的转换. 本文采用了一种新型有机二硫化物, 2,5-二硫基-1,3,4-噻二唑, 作为氧化还原介质, 其不仅能够利用其自身自均聚/自解聚反应来实现光电转换过程, 降低对电极的腐蚀, 而且在可见光区内的吸收很低, 也有利于制作背入射式的染料敏化太阳能电池体系. 通过器件的优化, 可以分别实现1.6% (100 mW·cm^-2)和2.6% (13 mW·cm^-2)的光电转换效率.     

含二级供电基团的三苯胺类光敏染料合成及太阳能电池中的应用

以N,N-二甲基苯胺作为二级给电子单元, 合成两种具有不同长度共轭链的三苯胺类光敏染料XS19和XS22. 研究了它们的光物理与光电化学性质, 并将它们用作TiO₂纳米晶电极的光敏化剂引入太阳电池, 结果表明, N,N-二甲基苯胺的引入能够抑制染料敏化太阳能电池中的电子复合, 提高电池的光电转换效率. XS22表现出更好的光伏性能, 在AM1.5 (100 mW•cm^－2)的光强下, XS22敏化电池的开路电压(V_OC)为685 mV, 短路电流密度(J_SC)为9.6 mA•cm^－2, 填充因子(FF)为0.72, 总光电转换效率为4.7%.     

含苯并噻二唑的吩噻嗪染料分子的设计合成及其在染料敏化太阳能电池中的应用

设计合成了三种含苯并噻二唑的吩噻嗪类有机染料光敏剂JY50~JY52,在对其光物理和电化学性质进行研究的基础上,使用三种染料对纳米TiO₂电极进行敏化制备太阳能电池器件,并系统研究了其光电转化效率及电荷传输阻抗等光伏特性.研究结果表明,在染料分子中引入共轭基团有助于其摩尔吸光系数的提升,从而提升光电流.两个长烷基链的引入能够有效地抑制染料分子激发态电子在TiO₂光阳极表面的电子复合,从而提升其电子注入效率.其中,在AM 1.5（100 mW·cm^-2）的模拟光强下,基于碘电解质的染料JY51电池器件获得了7.61%的光电转化效率.     

1-甲基-3-己基咪唑碘在染料敏化太阳电池中的应用研究

利用超微铂电极和循环伏安法, 以及电化学阻抗谱研究了在1-甲基-3-己基咪唑碘(HMII)的3-甲氧基丙腈(MePN)溶液中I₃^－和I^－的氧化还原行为, 并对比了由不同浓度的I₂和HMII组成的电解质溶液对染料敏化纳米薄膜太阳电池(DSCs)光伏性能的影响. 发现以MePN为溶剂, 含1.0 mol•dm^－3 HMII, 0.12 mol•dm^－3 I₂, 0.10 mol•dm^－3 LiI和0.50 mol•dm^－3 4-叔丁基吡啶的电解质溶液, 其DSCs的短路光电流密度为14.06 mA•cm^－2, 开路电压为0.71 V, 填充因子为0.69, 光电转换效率达6.81%.     

染料敏化太阳能电池对电极

对电极是染料敏化太阳能电池的重要组成部分,改进对电极是提高其能量转换效率及降低成本的有效手段之一.本文重点综述了2008年以来染料敏化太阳能电池对电极的研究成果,详细介绍了各类对电极包括金属Pt、Au、Ni,纳米炭材料和导电聚合物等对电极的优点和制备工艺.Pt对电极性能最好,但是高成本限制了它在染料敏化太阳能电池产业化中的应用;新型的价格低廉、活性较高的纳米炭材料和导电聚合物及其复合材料等对电极在染料敏化太阳能电池的研究中逐渐引起人们的重视.     

大面积全柔性染料敏化太阳能电池光电性能优化

设计并制作了大面积高效全柔性染料敏化太阳能电池（DSCs）.通过引入光散射层或施加机械压力,DSCs的光电转化效率有了大幅度提高.实验室小面积（0.4 cm×0.4 cm）柔性DSCs的光电转化效率达到5.50%.大面积（2 cm×3 cm,活性面积为2.7 cm²）DSCs的光电转化效率从未进行处理的1.52%上升到1.81%和2.50%,分别提高了20.0%和66.7%.5 cm×7 cm面积的DSCs（活性面积为16.2 cm²）的光是转化效率在未做任何优化处理的条件下达到了1.60%(光强40 mW·cm^-2).同时,本文对提高光电转化效率的机理进行了深入研究.电化学阻抗测试结果表明,加压法能明显减小电池的内部串联电阻（R_s）及TiO₂/染料/电解液界面间的传荷电阻(R_ct).扫描电镜结果也显示加压后TiO₂粒子之间粘结更加紧密,更利于电子在TiO₂薄膜中的传输及染料的吸附.另外,900 h的长期稳定性实验结果表明,制作的柔性DSCs的各项光电性能参数均无明显下降.该实验结果为柔性染料敏化太阳能电池的基础研究和大面积产业化技术研究奠定了基础.     

CoSe/TiN同轴纳米管阵列在染料敏化太阳能电池对电极中的应用研究

以钛网作为基底,采用阳极氧化、氨气氮化的方法制备了TiN纳米管,随后电沉积CoSe,制备了CoSe/TiN/Ti同轴纳米管阵列电极。循环伏安结果表明,CoSe/TiN/Ti电极对I-3具有高的电催化还原性能,这归因于高催化活性的CoSe和高导电的TiN的协同效应。以CoSe/TiN/Ti电极作为对电极组装染料敏化太阳能电池,电池的能量转换效率高达9.25%,比传统Pt/FTO对电极组装的电池(8.09%)高1%。这一结果为非Pt对电极纳米结构的设计提供了一个很好的思路。     

基于网状铂电极的新型柔性染料敏化太阳能电池

柔性染料敏化太阳能电池（DSSCs）作为一种新型的化学太阳能电池,因其精简的封装工艺、较低廉的价格、高的化学稳定性以及可弯折等优点而备受关注. 本文介绍了一种新型的柔性DSSC的制备,其光阳极为高度有序的氧化锌（ZnO）纳米线阵列,对电极为柔性、导电、透明的网状铂(Pt networks)电极. 相对于传统的铂对电极而言,这种Pt networks对电极不仅具有优异的导电能力,还展现了极好的透光性（方阻~ 100 Ω•sq^-1,~80%透光率）和催化性能,此外,Pt networks电极可构筑于任意弯曲的衬底,具有优异的机械耐弯折性能. 在ZnO纳米线阵列的DSSCs的应用中,基于Pt networks膜的柔性DSSC的转化效率比铂纳米丝阵列 (Pt nanofiber arrays, Pt NFs）膜高出了32%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.