新型水氧化催化剂的制备与性质研究

项目名称： 新型水氧化催化剂的制备与性质研究

项目编号： No.21331007

项目类型： 重点项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 鲁统部

作者单位： 天津理工大学

项目金额： 310万元

中文摘要： 利用太阳光在催化剂作用下催化分解水制备氢气和氧气具有重要的研究意义，其中水的催化氧化是光解水制氢的瓶颈和关键，而降低水的氧化电位是催化水氧化研究亟待解决的关键问题。我们此前发现一种含蒽环氮杂大环化合物在光照下能够催化氧化水为氧气，并还原Cu(II)为Cu(I)，表明水的氧化可在较低电位下实现。本项目针对这一独特的反应现象，继续对上述反应过程和机理进行深入系统的研究。拟合成系列含有蒽环、苝环及其衍生物等基团的氮杂大环化合物，通过循环伏安、光催化水氧化等步骤对合成的催化剂的催化转化速率(TOF)和催化效率（TON）进行评价，对催化剂的结构和催化活性之间的构效关系进行研究。通过ESR、XPS、ESI-MS和量化计算等对上述催化剂催化水氧化的活性物种和过渡态进行跟踪和推测，并结合构效关系的结果给出合理的催化机理。

中文关键词： 氮杂大环化合物;光催化水氧化；;水分解;催化剂;反应机理

英文摘要： Splitting water into H2 and O2 using sunlight and catalysts is extremely important to our society, in which the water oxidation step is currently considered as the bottleneck of the water-splitting process, and decrease the potentials of water-oxidation is a fundamental question and urgent theme to be solved. We have previously found that a protonated organic cryptand containing anthracene fragment can oxidize water into oxygen under UV-light, and reduce CuII to CuI, indicating the water-oxidation can be achieved under low potentials. In this project, we will continue to study the above unique reaction, and we will synthesize a series of aza macrocyclic compounds containing anthracene, pyrene groups, as well as their derivants. The TON and TOF of the above synthesized catalysts will be measured during electrocatalytic and light-driven catalytic processes, and the relationship between structures of catalysts and the catalytic effect will be summarized based on the TOF and TON data. The active species and intergrade will be monitored and investigated using ESR, XPS, ESI-MS and DFT calculations, and the reasonable catalytic process and mechanism will be given based on the above investigations.

英文关键词： aza macrocyclic compounds;light-driven water-oxidation;water-splitting;catalyst;reaction mechanism