用于醇类催化氧化的非金属碳纳米量子点催化剂的合成与性能研究

Stoichiometric oxidants, such as chromic acid and permanganic acid, which have been widely used in the traditional aerobic oxidation of alcohols, have brought serious environmental concerns owing to the disadvantages such as complexity, toxicity of the raw marerials, equipment corrosion and unrecyclable process. To overcome the issues, the key is to design effective catalysts for the aerobic oxidation under mild conditions in the presence of molecular oxygen. The carbon nanotubes supported metal oxides catalysts we developed previously showed high catalytic acitivities for aerobic oxidation of alcohols. However, the application was limited by the high cost of the catalysts. Thus, the development of novel inexpensive non-metal solid-phase catalyst is of significant importance for the aerobic oxidation of alcohols in fine chemical industry. With this in mind, we propose to synthesize the carbon quantum dots by the chemical oxidation method using carbon black or activated carbon as the precusors for the aerobic oxidation of alcohols. The proposed work includes: (a) clarify the effect of particle size, surface functional groups and surface modifications of the carbon quantum dots on the catalytic activity, and build the structure-property relationship of the carbon quantum dots. (b) illucidate the catalytic mechanism of for the aerobic oxidation of alcohols by tracking the changes of the carbon quantum dots (with the extraordinarily optical properties) via in-situ FT-IR and UV-VIS studies. Our research will provide new thinking and methods for the development and design of non-metal catalyst for the aerobic oxidation of alcohols.

传统的醇类液相催化氧化体系采用铬、锰等重金属化学计量氧化剂，存在反应体系复杂、自身毒性、设备腐蚀、催化剂难以回收等弊端，对环境造成很大危害。寻求能有效活化分子氧的固相催化剂被认为是解决这一问题的关键。前期研究工作显示，采用负载型贵金属或贵金属氧化物的确能获得较高的催化性能，但贵金属类催化剂成本较高，很难从根本上解决问题。因此，寻求非金属类固相催化剂就成为目前精细化工领域醇类催化氧化的热点。 本项目采用碳黑或活性炭作为碳源，以强酸氧化法一步合成碳纳米量子点，以环境友好的醇类液相催化氧化过程为目标，测试其催化氧化性能，系统研究碳纳米量子点尺寸大小、表面基团以及表面改性对催化剂活性及选择性的影响，从而获得其结构与性能之间的构效关系。通过利用碳纳米量子点特殊的光学性能，采用原位光谱方法在线监测反应过程，获取反应机理，为设计和开发新型非金属类醇类催化氧化催化剂提供思路和方法。

传统的醇类液相催化氧化体系采用铬、锰等重金属化学计量氧化剂，存在反应体系复杂、自身毒性、设备腐蚀、催化剂难以回收等弊端，对环境造成很大危害。寻求能有效活化分子氧的固相催化剂被认为是解决这一问题的关键。前期研究工作显示，采用负载型贵金属或贵金属氧化物的确能获得较高的催化性能，但贵金属类催化剂成本较高，很难从根本上解决问题。因此，寻求非金属类固相催化剂就成为目前精细化工领域醇类催化氧化的热点。.本项目采用碳黑或活性炭作为碳源，以强酸氧化法或者电化学法一步合成了碳纳米量子点，以环境友好的醇类液相催化氧化过程为目标，测试了其催化氧化性能，系统研究了碳纳米量子点尺寸大小、表面基团以及表面改性对催化剂活性及选择性的影响，从而获得了结构与性能之间的构效关系。通过利用碳纳米量子点特殊的光学性能，采用原位光谱方法在线监测反应过程，获取了反应机理，为设计和开发新型非金属类醇类催化氧化催化剂提供了思路和方法。