固载模拟[Fe-Fe]氢化酶在纯水体系中的产氢及电子转移过程研究

项目名称： 固载模拟[Fe-Fe]氢化酶在纯水体系中的产氢及电子转移过程研究

项目编号： No.21302196

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 于天君

作者单位： 中国科学院理化技术研究所

项目金额： 25万元

中文摘要： 模拟自然界光合作用，发展高效太阳能光催化产氢体系一直是化学家研究的重点之一。随着人们对自然界氢化酶结构解析精度的提高，氢化酶的化学模拟以及光驱动产氢成为研究的新热点。人工模拟[Fe-Fe]氢化酶的催化活性普遍较低，有效的电荷分离被认为是提高模拟氢化酶催化活性的重要因素。寻找适合的方法延长电荷分离态寿命，提高模拟氢化酶的稳定性和催化活性成为太阳能光催化制氢研究中的重要内容。此外，人工模拟氢化酶大都不溶于水，建立一种有效且通用的方法突破模拟氢化酶对有机溶剂的依赖也是非常必要的。本项目将模拟氢化酶固载到水凝胶或分子筛载体上，应用于纯水环境光催化产氢，研究载体对模拟氢化酶催化性质和光敏剂与模拟氢化酶间的电子转移过程的影响，载体对模拟氢化酶和通过电子转移生成的模拟氢化酶离子自由基中间体(电荷分离态)的稳定化作用，以及固载人工模拟氢化酶在水中光催化产氢应用，为模拟氢化酶纯水催化体系的构筑提供新的思路。

中文关键词： 氢化酶；能量转换；固载；产氢；光化学

英文摘要： The requirement to develop inexpensive renewable energy sources has stimulated new approaches to establish light-induced hydrogen production system in conversion and storage of solar energy. Hydrogen photoproduction through mimicking natural photosynthesis is considered to be one of the most attractive and potential means. Since the biological structures and the functionalities of the active sites of hydrogenases were proposed, the diiron hydrogenase modeling has shown a very blooming development in photochemical hydrogen production. However, none of these hydrogenase mimics show catalytic activities as high as natural hydrogenases do, and the effective charge separation has been considered to be a key factor in photochatalytic hydrogen evolution. The construction of robust hydrogenase models with high photocatalytic activity and efficiency remains a great challenge. Moveover, it is essential to develope a universal method to overcome their poor solubility in water. In this project, the hydrogenase mimics will be immobilized to hydrogel or molecular sieve, which will be applied in pure water for hydrogen photoproduction. The activity of the immobilized hydrogenase mimics for hydrogen evolution, and the electron transfer process will be investigated. The stabilizing effect of the supports on the hydrogenase mimic

英文关键词： Hydrogenase；energy conversion；immobilization；hydrogen photoproduction；photochemistry