磁性纳米材料负载金属氮杂卟啉催化剂的设计及其活化分子氧绿色氧化液态醇的研究

Designing high catalytic activities and long-life catalysts for the selective oxidation of alcohols to the corresponding carbonyl compounds with molecular oxygen is a very important goal for organic industry. In this project, we will firstly carry out the study of oxidation of alcohols in the presence of oxygen catalyzed by the prepared metal porphyrazines as mimic enzyme catalysts, and find some precursors with higher activity and selectivity to construct the subsequent solid catalysts. Then, those metal porphyrazines with higher catalytic activity will be designed to bond on surface of the magnetic Fe3O4@SiO2 particles with core-shell structure as supported catalysts, and will be used for the selevtive oxdiation of aicohols in water or solvent free system. Through further modifying the structure of the catalysts and optimizing the oxidation conditions, a novel biomimetic catalytic system will be constructed for the selective oxidation of alcohols with high yield and high selectively. In addition, the mechanism of the selective oxidation of alcohols will be studied by spectroscopies, isotope labeling, and EPR radical capture technologies and so on. In this project, the processes of catalysts preparation and recycle are simplified with the external magnetic force. More importantly, the sulfur-containing porphyrazine molecules are grafted on the surface of Fe3O4@SiO2 particles with organic space, thus it will avoid the molecules aggregation and destruction due to self oxidation. Moreover, the molecules are suspended on the surface of the support, which provide a similar homogenous environment for the alcohol oxidation. The value of this project will provide a novel research idea for the selective oxidation of alcohols to obtain corresponding carbonyl compounds, and it will also provide some scientific thought for sustainable development of the economy and the environment in the organic industry.

发展高活性、长寿命的催化剂用于活化分子氧选择性氧化醇制备醛、酮是有机工业的重要研究目标。本项目拟将合成的系列含硫四氮杂金属卟啉作为模拟酶催化剂，在水相或无溶剂条件下活化分子氧选择氧化液态醇，筛选出其中活性和选择性较为理想的含硫四氮杂金属卟啉。再行设计出核壳型磁性Fe3O4@SiO2纳米材料经化学键合具有较高活性的含硫氮杂金属卟啉的负载型催化剂，开展在水相或无溶剂体系中模拟酶活化分子氧选择性氧化醇。通过进一步修饰催化剂结构和优化工艺条件，实现高效、高选择性的新型醇的催化氧化体系。同时借助光谱学、同位素标记、EPR自由基捕获技术等手段探究反应机理。该方法催化剂制备及回收简单，且卟啉分子被有机短链键合在磁性材料表面，可避免自身降解和聚合，能"悬浮"于反应体系中具有类均相性质。本项目的实施与完成可为醇的选择性氧化制备醛、酮提供新的研究思路，为有机行业的环境和经济可持续发展提供科学思想。

发展系列高活性、长寿命的催化剂用于活化分子氧或过氧化氢选择性氧化醇制备醛、酮或酸，是有机工业的重要研究目标。本项目合成了系列含硫四氮杂金属卟啉作为模拟酶催化剂，在水相中活化分子氧或过氧化氢选择氧化液态醇，筛选出了其中活性和选择性较为理想的不对称含硫四氮杂金属卟啉，如六（正丁硫基）-（1,4-二噻英）四氮杂铁卟啉（FePz(SBu)6(dtn)）和六（正丁硫基）-（对甲氧基苯并）四氮杂锰卟啉，（MnPz(SBu)6(phOMe)）。再行设计出核壳型磁性Fe3C@CNTN纳米材料负载、或g-C3N4或Al2O3负载的具有较高活性的含硫氮杂金属卟啉的负载型催化剂，开展在水相体系中模拟酶活化分子氧或过氧化氢选择性氧化醇。通过进一步修饰催化剂结构和优化工艺条件，实现高效、高选择性的新型醇的催化氧化体系，如热催化氧化苯甲醇到苯甲醛经6小时产率可达80%，选择性可达100%，光催化氧化苯甲醇到苯甲酸经12小时可达73%，选择性100%，TON接近700。光催化氧化一些特殊有机醇如生物质衍生品5-羟甲基糠醛到呋喃二酸产率经14小时可达97%。同时借助光谱学、EPR自由基捕获技术等手段探究了反应机理。该方法催化剂制备及回收简单，可避免自身降解和聚合，能“悬浮”于反应体系中具有类均相性质。本项目已经发表论文16篇，其中SCI论文6篇，国内核心期刊论文3篇，会议论文6篇，申请发明专利1项。合成出新的含硫氮杂卟啉配体9个，其中得到了三个晶体结构；活性亚砜中间体1个；二个新的TEMPO与铜的配合物的晶体结构，得到了二种新的镶嵌有含硫四氮杂金属卟啉聚合物纳米球和纳米球壳的方法。本项目的完成为醇的选择性氧化制备醛、酮或酸提供了新的研究思路，为有机行业的环境和经济可持续发展提供科学思想。