类贵金属CoN@C催化剂可控制备及其催化伯醇和仲醇氧化偶联制备α,β-不饱和酮反应的研究

项目名称： 类贵金属CoN@C催化剂可控制备及其催化伯醇和仲醇氧化偶联制备α,β-不饱和酮反应的研究

项目编号： No.21503219

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 张磊磊

作者单位： 中国科学院大连化学物理研究所

项目金额： 20万元

中文摘要： α,β-不饱和酮是重要的有机合成中间体，广泛应用于医药、农药、香料等精细化学品合成中。鉴于传统的合成方法存在选择性差、原子经济性低等缺点，本项目提出以伯醇、仲醇、O2为原料，“一锅”制备α,β-不饱和酮的新途径，并为该反应设计制备兼具高活性和高选择性且组成单一的类贵金属CoN@C催化剂。以实验和理论相结合的方法，（1）考察不同的制备参数对催化剂组成和结构的影响规律，并以伯醇和仲醇氧化偶联制备α,β-不饱和酮为目标反应对催化剂进行活性评价，同时结合先进的表征技术，研究催化剂结构、组成与性能之间的关系，以实现高活性CoN@C催化剂的可控制备；（2）通过理论计算研究催化剂对O2的吸附活化行为，为拓宽在其它氧化反应中的应用提供理论依据。所得研究结果，在基础研究领域将加深对CoN@C催化剂具有“类贵金属”催化行为的认识，在工业应用方面将为α,β-不饱和酮的合成提供新的方法和高效的非贵金属催化剂。

中文关键词： CoN@C催化剂；可控制备；伯醇和仲醇；氧化偶联；α；β-不饱和酮

英文摘要： α,β-unsaturated ketones are key intermediates widely used in pharmaceutical, agrochemical, perfume and other fine chemical industries. The traditional synthesis of α,β-unsaturated ketones suffer from poor selectivity and low atomic economy. On this ground, this project aim to develop a “one-pot” strategy to produce α,β-unsaturated ketones through aerobic oxidative coupling of primary and secondary alcohols, and to explore a type of “platinum-like” CoN@C based catalysts with uniform composition that are expected to be highly active and selective for the target reaction. In this project, we will combine experimental and theoretical methods, (1) to study the effect of different preparation parameters on the structure and composition of CoN@C based catalysts, and the catalytic performances of CoN@C catalysts in aerobic oxidative coupling of primary and secondary alcohols to produce α,β-unsaturated ketones, meanwhile by combining the characterization results to clarify the structure-performance relationship, in order to realize the controllable synthesis of highly active and selective CoN@C based catalysts; (2) to investigate the adsorption and activation behavior of O2 on the active species of CoN@C catalysts by DFT calculations, in order to expand the application of CoN@C catalysts into other oxidative transformations. This program will not only contribute to the understanding the catalytic behavior of “platinum-like” CoN@C catalysts in aerobic oxidative reactions, but also provide a practical avenue for the development of efficient noble-metal-free catalysts for green synthesis of α,β-unsaturated ketones.

英文关键词： CoN@C based catalysts;controllable preparation;primary and secondary alcohols;aerobic oxidative coupling;α;β-unsaturated ketones