High-performance dye-sensitized solar cells based on solvent-free electrolytes produced from eutectic melts

Low-cost excitonic solar cells based on organic optoelectronic materials are receiving an ever-increasing amount of attention as potential alternatives to traditional inorganic photovoltaic devices. In this rapidly developing field, the dye-sensitized solar cell(1) (DSC) has achieved so far the highest validated efficiency of 11.1% (ref. 2) and remarkable stability(3).

New Organic Sensitizer for Stable Dye-Sensitized Solar Cells with Solvent-Free Ionic Liquid Electrolytes

We report a high molar extinction coefficient metal-free sensitizer composed of a triarylamine donor in combination with the 2-(2,2'-bithiophen-5-yl)acrylonitrile conjugation unit and cyanoacrylic acid as an acceptor. In conjugation with a volatile acetonitrile-based electrolyte or a solvent-free ionic liquid electrolyte, we have fabricated efficient dye-sensitized solar cells showing a corresponding 7.5% or 6.1% efficiency measured under the air mass 1.5 global sunlight. The ionic liquid cell exhibits excellent stability during a 1000 h accelerated test under the light-soaking and thermal dual stress. Intensity-modulated photocurrent and photovolatge spectroscopies were employed along with the transient photoelectrical decay measurements to detail the electron transport in the mesoporous titania films filled with these two electrolytes.

Dye-sensitized solar cells with solvent-free ionic liquid electrolytes

We systematically studied the temperature-dependent physicochemical properties, such as density, conductivity, and fluidity, of 1,3-dialkylimidazolium iodides. In combination with the amphiphilic Z907Na sensitizer, we have found that it is important to use low-viscosity iodide melts with small cations to achieve high-efficiency dye-sensitized solar cells. By employing high-fluidity eutectic-based melts the device efficiencies considerably increased compared to those for cells with the corresponding state of the art ionic liquid electrolytes.

N-Methyl-N-Allylpyrrolidinium Based Ionic Liquids for Solvent-Free Dye-Sensitized Solar Cells

We prepared four new ionic liquids consisting of N-methyl-N-allylpyrrolidinium cation in conjunction with anions including iodide, nitrate, thiocyanate, and dicyanamide, respectively, and measured their physical properties of density, viscosity, and conductivity. Owing to the relatively lower melting point of electroactive N-methyl-N-allylpyrrolidinium iodide, in combination with three other nonelectroactive ionic liquids, we could construct solvent-free electrolytes possessing high iodide concentrations for dye-sensitized solar cells. We correlated temperature-dependent electrolyte viscosity with molar conductivity and triiodide mobility through applying an empirical Walden's rule and a modified Stokes-Einstein equation, respectively. We have further found that these anions (nitrate, thiocyanate, and dicyanamide) have different influences on surface states and electron transport in the mesoporous titania film, resulting in different photovoltages and photocurrents of dye-sensitized solar cells.

Cyclohexane oxidation on a novel Ti70Zr10Co20 catalyst containing quasicrystal

Ti70Zr10Co20 containing an icosahedral quasicrystalline phase has been fabricated, and presents high activity and selectivity in catalyzing the oxidation of cyclohexane with oxygen under solvent-free conditions.

Mild and efficient copper-catalyzed N-arylation of alkylamines and N-H heterocycles using an oxime-phosphine oxide ligand

A mild and efficient copper-catalyzed system for N-arylation of alkylamines and N-H heterocycles with aryl iodides using a novel, readily prepared and highly stable oxime-functionalized phosphine oxide ligand was developed. The coupling reactions could even be performed in solvent-free conditions with moderate to good yields. (c) 2005 Elsevier Ltd. All rights reserved.

氮杂环化合物的绿色合成研究

氮杂环化合物大多数都是具有生理活性的物质，例如喹喔啉化合物与苯二氮卓类化合物，因此研究氮杂环化合物骨架的构建方法具有一定意义。绿色化学的迅速发展迫切要求化学家发展清洁、经济和环境较友好条件下的有机合成方法。其中，水相反应与绿色固体酸催化剂的使用都是实现绿色有机合成的重要途径，它们非常具有潜力，近些年受到了广泛关注。本论文的主要工作是围绕水相及固体酸催化条件下两类具有生物活性的含氮杂环小分子的合成方法而开展的，具体包括以下内容： 1. 研究和探索出了两类绿色固体酸催化剂蒙脱土（Mont. K-10）和杂多酸(H4SiW12O40), 在水相条件下成功合成出喹喔啉化合物的有效方法。两个催化体系都以无毒无公害的水作反应溶剂，实验条件温和，操作安全简便，反应速度快，底物普适性强，产率高，且产物易分离收集。两类固体酸催化剂，对设备腐蚀性小，可回收循环使用，对环境无公害; 蒙脱土催化大部分底物能得到当量产率的产物，硅钨酸催化催化剂负载量小。 2. 实现了无溶剂条件下，以杂多酸（H3PW12O40）作催化剂，高效合成1,5-苯二氮卓衍生物的合成方法。该催化体系具有以下一些优势：实验条件温和，反应速度较快，底物普适性良好，产物易分离收集，反应过程中没有加入其它有机溶剂，绿色环保。 ‘Green Chemistry’ is currently a major issue of modern chemistry. It is widely acknowledged that there is a growing need for more environmentally acceptable processes in the chemical industry. New green catalysts and green reaction media are the important and efficient strategies in green chemistry. New green catalysts include solid acid catalysts, solid base catalysts, metal catalysts not only possess higher activity and selectivity, but also are easily separated from reaction system. Green reaction media include water, supercritical fluids and ionic liquids can not only substitute traditional toxic and harmed organic solvents, but also improve reaction activity and selectivity. Meanwhile water is a promising green reaction medium for use in modern chemistry because it has a number of advantages such as the cheapest solvent available on earth, being non-hazardous and non-toxic to the environment. Solid acids had also attracted much attention for realizing green chemistry due to their unique acidity, high activity and efficiency as organic catalysts. Nitrogen-containing heterocyclic compounds of different ring sizes such as quinoxaline and benzodiazepine are the important pharmacologically active compounds. Due to the wide biological significance of these compounds, the synthesis of these types of compounds have received a great deal of attention. Despite the large availability of methods to construct nitrogen-containing heterocyclic compounds, there is still a strong need to further explore green methods to efficiently and safely synthesize these compounds. Thus, we aim at developing efficient and green methodology for the synthesis of quinoxaline and benzodiazepine carried out under water condition with solid acid catalysts. The contents of this dissertation are listed as the following: 1. We have developed two catalytic systems for the synthesis quinoxaline via the condensation of an aryl 1,2-diamine with a 1,2-diketone compound in the presence of Mont. K-10 or H4SiW12O40 as a catalyst in water solvent. Both of these two methods can be applied to wide range of substrates, tolerating aryl 1,2-diamine/1,2-diketone with the electron donating/drawing substituent. Operational simplicity, the ambient conditions, use of an economically convenient catalyst, use of water as a desirable solvent, high yields and short reaction times are the key features of these two protocols. 2. We developed a convenient and efficient protocol for the synthesis of a variety of 1,5-benzodiazepines in high yields via condensation of aryl o-phenylenediamine derivatives with a variety of ketones using H3PW12O40 as a green recyclable and heterogeneous catalyst under solvent-free condition. The simple experiment procedure combined with ease of recovery and reuse of this catalyst make this procedure quite simple, more convenient and environmentally benign.

High-Performance Liquid and Solid Dye-Sensitized Solar Cells Based on a Novel Metal-Free Organic Sensitizer

A new metal-free organic sensitizer (see figure) for high-performance and applicable dye-sensitized solar cells is presented. In combination with a solvent-free ionic liquid electrolyte, a similar to 7% cell made with this sensitizer shows all excellent stability measured under thermal and light-soaking dual stress. For the first time a 4.8% efficiency is reached for all-solid-state dye-sensitized solar cells based oil all organic dye.

Interactions of Penny-Shaped Cracks in Three-Dimensional Solids

The interaction of arbitrarily distributed penny-shaped cracks in three-dimensional solids is analyzed in this paper. Using oblate spheroidal coordinates and displacement functions, an analytic method is developed in which the opening and the sliding displacements on each crack surface are taken as the basic unknown functions. The basic unknown functions can be expanded in series of Legendre polynomials with unknown coefficients. Based on superposition technique, a set of governing equations for the unknown coefficients are formulated from the traction free conditions on each crack surface. The boundary collocation procedure and the average method for crack-surface tractions are used for solving the governing equations. The solution can be obtained for quite closely located cracks. Numerical examples are given for several crack problems. By comparing the present results with other existing results, one can conclude that the present method provides a direct and efficient approach to deal with three-dimensional solids containing multiple cracks.

Analysis of two-dimensional finite solids with microcracks

A general method is presented for solving the plane elasticity problem of finite plates with multiple microcracks. The method directly accounts for the interactions between different microcracks and the effect of outer boundary of a finite plate. Analysis is based on a superposition scheme and series expansions of the complex potentials. By using the traction-free conditions on each crack surface and resultant forces relations along outer boundary, a set of governing equations is formulated. The governing equations are solved numerically on the basis of a boundary collocation procedure. The effective Young's moduli for randomly oriented cracks and parallel cracks are evaluated for rectangular plates with microcracks. The numerical results are compared with those from various micromechanics models and experimental data. These results show that the present method provides a direct and efficient approach to deal with finite solids containing multiple microcracks.

Experimental Study Of Vortex-Induced Vibrations Of A Pipeline Near An Erodible Sandy Seabed

Based on similarity analyses, a series of experiments have been conducted with a newly established hydro-elastic facility to investigate the transverse vortex-induced vibrations (VIVs) of a submarine pipeline near an erodible sandy seabed under the influence of ocean currents. Typical characteristics of coupling processes between pipe vibration and soil scour in the currents have been summarized for Case 1: pipe is laid above seabed and Case 11: pipe is partially embedded in seabed on the basis of the experimental observations. Pipe vibration and the corresponding local scour are usually two coupled physical processes leading to an equilibrium state. The influence of initial gap-to-diameter ratio (e(0)/D) on the interaction between pipe vibration and local scour has been studied. Experimental results show that the critical values of V-r for the initiation of VIVs of the pipe near an erodible sand bed get bigger with decreasing initial gap-to-diameter ratio within the examined range of e(0)/D (-0.25 < e(0)/D < 0.75). The comparison of the pipe vibrations near an erodible soil with those near a rigid boundary and under wall-free conditions indicates that the vibration amplitudes of the pipe near an erodible sand bed are close to the curve fit under wall-free conditions; nevertheless, for the same stability parameter, the maximum amplitudes for the VIV coupled with local scour increase with the increase of initial gap-to-diameter ratio. (c) 2007 Elsevier Ltd. All rights reserved.