二氧化钛表面络合物诱导的可见光光催化选择性氧化反应

项目名称： 二氧化钛表面络合物诱导的可见光光催化选择性氧化反应

项目编号： No.21503086

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 有机化学

项目作者： 郎贤军

作者单位： 华中师范大学

项目金额： 21万元

中文摘要： 为了应对能源危机和全球变暖的影响，清洁太阳能源的捕获和利用已成为化学研究的重要主题。其中，利用可见光实现温和条件下的有机物选择性氧化是清洁太阳能源的捕获和利用的重要途径。然而，二氧化钛不能直接吸收可见光，无法实现可见光反应。本项目利用含有杂原子有机底物（如醇、胺和硫类化合物）与二氧化钛纳米晶相互作用可以直接产生吸收可见光的表面络合物活化有机底物，构建室温可见光催化有机合成方法，在可见光下利用分子氧为氧源实现含杂原子类有机底物的选择性转化。项目通过反应条件的控制来提高表面络合物诱发的苄醇和苄胺选择性转化反应活性，获取其反应动力学信息；将底物范围能否拓宽到脂肪醇和无苄基的脂肪胺以及硫醚；并利用表面络合物诱发硫酚和苯胺类化合物氧化为二硫和偶氮化合物，将一些常温下原本无法实现的有机转化反应变为可能。项目的实施将有助于我们深入理解二氧化钛光催化的过程，为未来的高效光催化氧化反应的发展提供基础。

中文关键词： 二氧化钛；光催化；可见光；选择性氧化；分子氧

英文摘要： To meet the challenges of energy crisis and to mitigate the impact of global warming, the harvesting and application of clean solar energy is one of the most current topics in chemical research. Amongst many aspects of research along this line, visible-light-induced organic transformations under very mild conditions place a very important position. Ideally, it is very interesting to carry out these reactions with titanium dioxide, which cannot absorb visible-light directly. To this end, the unique visible-light absorption phenomena of the interaction of heteroatom-containing substrates such as alcohols, amines and sulfides with titanium dioxide is explored for efficient organic redox transformations under visible-light irradiation. As a result, new synthetic methods are created for transformation of heteroatom-containing substrates under visible-light irradiation at room temperature with molecular oxygen as the terminal oxidant. The reaction details will be followed and discerned for the oxidation of benzylic alcohols and amines. Through rigorous control, the substrate scopes can be expanded to aliphatic alcohols, non-benzylic aliphatic amines and thioanisoles. Furthermore, disulfides and azo compounds can be synthesized by the aerobic oxidation of thiophenols and anilines on titanium dioxide under visible-light irradiation. More interestingly, some reactions, which cannot be realized under UV irradiation, could be transcended into reality with visible-light irradiation. Through this project, we can understand the mechanism of the photo-induced processes through a unique perspective aiming at highly efficient visible-light-induced aerobic oxidation with titanium dioxide as the photocatalyst.

英文关键词： titanium dioxide;photocatalysis;visible-light;selective oxidation;molecular oxygen