低聚卟啉与锚定卟啉分子轴向配位组装敏化太阳能电池电极

Dye-sensitized solar cells (DSSC) are an attractive solar energy conversion technology and their advantages include their high power conversion efficiency, low production cost, and simplicity of fabrication. Among the various synthetic dyes, porphyrins have been considered to be promising candidates for DSSC because of their superior light-harvesting ability in the visible region, easy chemical tuning of their physical properties and environmental friendliness. The key to achieving highly efficient DSSC lies in the design and synthesis of stable organic dyes with appropriate push−pull structure. Based on our previous research on DSSC, we will design and synthesize novel porphyrin oligomers, which will be locked onto TiO2 /FTO surface through anchoring porphyrin molecules , then addition of electrolyte to form dye-sensitized solar cells . The electron-rich conjugated moieties as the speotrum adjusting antennas will be combined directly on porphyrin systems, which will possess broadening and a red shift of the absorption bands. Using iodide/triiodide redox couple as reference electrolyte, seek for transitionmetal complexes electrolyte with pridine-azole ligands, which is more better inhibition of back electron transfer. So resulting in enhancement of power conversion efficiency. Systemically investigate the correlativity between the photoelectronic performance and the structures of porphyrin-oligomer, anchoring molecules, co-sensibilizer or complex redox shuttle. Setup a method for optimizing the photo-to-electric power-conversion efficiency of porphyrin-oligomers system, explore mechanism of photoelectron generation and transport, to develop novel high efficiency dye-sensitizer material for DSSC.

染料敏化太阳能电池（DSSC）是一种高效率、低成本、制做简单的新型电池。卟啉具有优异的光捕获能力、容易化学调节物理性质和环境友好等而成为有前景的染料敏化剂。获取高效敏化电池的关键是设计合成具有适当“推-拉”结构的稳定染料。本项目在前期DSSC研究基础上，拟设计合成新型卟啉低聚物，该低聚物经卟啉锚定分子锁定到TiO2/FTO表面，加注电解质后组成敏化电池。将共轭基团作为光谱调节天线直接引入卟啉体系，加宽卟啉对太阳辐射的吸收范围。以电对I3-/I-的电解质溶液作参比，探寻能有效阻止光电子逆向转移的吡啶-氮唑类过渡金属配合物电解质。提高组装体系的光电转化效率。系统研究卟啉低聚物、锚定分子、共敏化分子和配合物电解质的结构对光电性能的影响。建立优化低聚卟啉配位组装体系光电转化效率的方法，揭示各界面间电子传递机理。开发新型的DSSC高效敏化材料。

在染料敏化太阳能电池(DSSCs)中，染料敏化剂是重要的组成部分。具有适当“推-拉”结构的卟啉敏化剂受到了广泛关注和研究。卟啉的轴向配位自组装超分子体系也为DSSCs的设计策略提供了新的思路。.本项目在前期DSSC研究基础上，设计合成新型锌卟啉含有不同基团的双酰腙锰配位聚合物作天线卟啉体系，与含吡啶的卟啉羧酸锚定分子（ZnPA）通过轴向配位组装锁定到TiO2/FTO表面，组成DSSC敏化电池。研究表明双酰腙锌卟啉锰配聚物-ZnPA体系比单一的锚定分子ZnPA（2.03%）的效率都有较大提升，尤其是含三氟甲基的双酰腙锌卟啉（3.33%）。进一步考查了应用含吡啶的酰腙金属卟啉组装钙钛矿太阳能电池，铜卟啉（18.21%）优于锌卟啉（17.76%）且都给出了很高的稳定性尤其是热稳定性。.由于锚定卟啉的重要作用，注重研究了锚定卟啉分子的修饰基团对光电性能的影响。首先开展了卟啉meso-位不同基团修饰的吡啶卟啉羧酸锚定分子，研究表明含对叔丁基苯基能显著提高锚定分子的光电效率（3.85%），再与A4三氟甲基苯锌卟啉轴向配位后，组装体给出更高的效率（4.26%）。其次对锚定卟啉的羧酸基团部分进行了设计合成优化。结果表明含对炔基苯烯腈基甲酸的锚定卟啉有较高的效率（3.27%）。.对于配位组装方式的探索，联吡啶钌配合物与锚定卟啉的组装体，通过共敏化得到提升的光电效率。意味着卟啉羧酸锚定分子（ZnPA）被联吡啶钌配合物作为天线配合物组装后优化了效率（3.39%）。.机理研究，通过光谱分析，电化学阻抗，膜电极形貌，用DFT/TD-DFT两种理论对自组装敏化剂进行了研究，揭示各界面间电子传递机理。分析了抑制电荷在 TiO2表面的复合，使电池的开路电压和短路电流密度可得到提高的因素。阐明了卟啉组成结构与光电效率的关系。对开发实用的DSSC高效敏化材料有重要指导意义。