杂多酸@介孔氮化碳高效催化无还原剂苯-O2羟基化制苯酚

项目名称： 杂多酸@介孔氮化碳高效催化无还原剂苯-O2羟基化制苯酚

项目编号： No.21476109

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 有机化学

项目作者： 王军

作者单位： 南京工业大学

项目金额： 90万元

中文摘要： 苯直接一步羟基化制苯酚是至今未得到实际应用的绿色化工工艺，原子经济的无牺牲性还原剂非贵金属催化的液相苯-O2羟基化制苯酚更是极具挑战性的难题。基于申请人在液相苯羟基化及杂多酸催化剂研究中的长期积累和进展，本项目提出设计和制备由含V杂多酸(Keggin结构PMoV2及Dawson结构P2W15V3)和介孔类石墨烯结构的氮化碳(mC3N4)形成的一体式复合催化剂：即离子键链接的PMoV2@mC3N4和共价键链接的P2W15V3@mC3N4，旨在实现无还原剂苯-O2羟基化制苯酚的高效多相催化新工艺。重点研究催化剂的设计和制备，组成结构和物化性质，以及催化活性和稳定性；结合表征分析深入认识氮化碳活化苯环和杂多酸活化分子氧的双活性中心机理，揭示催化剂电子因素、孔结构、双活性中心分布与协同，以及有机链接体对催化性能的影响机制，为构建廉价高效苯-O2羟基化制苯酚绿色多相催化工艺提供新途径和科学基础。

中文关键词： 苯羟基化制苯酚；催化剂设计；类石墨烯结构氮化碳；杂多酸；构效关系

英文摘要： One-step direct hydroxylation of benzene to phenol is a much desirable green process, but it has not been brought into practical utilization up to date. In this context, molecular oxygen O2 is a cheap oxidant with the highest atomic economy, however, the non-noble metal-catalyzed liquid-phase benzene hydroxylation with O2 in the absence of a sacrificial reductant remains a highly challenging issue. Based on the long-term experiences and the already obtained results on the hydroxylation reaction of benzene and heteropolyacid (HPA) catalysts, the applicant of this project designs and prepares the dual catalysis center-combined catalysts from the V-HPAs (Keggin-structured PMoV2 and Dawson-structured P2W15V3) and mesoporous g-C3N4 (mC3N4), i.e., the ionic bond-linked PMoV2@mC3N4 and covalent bond-linked P2W15V3@mC3N4. The two catalysts aim to highly efficiently catalyze the liquid-phase benzene hydroxylation with O2 in the absence of a sacrificial reductant with convenient catalyst recovery and reuse. Catalyst design and preparation, composition and structure, physical and chemical properties, and catalytic activities and stability, will be studied. Together with catalyst characterizations, the dual-catalysis mechanism where the benzene ring is activated by mC3N4 and the molecular oxygen by V-HPAs will be investigated and recognized. Further, influences of catalytic performances by key parameters will be elucidated, such as electronic effect, pore structure, distribution and synergy of the two active sites, and the organic linkers, based on which structure-activity relationship is discussed. This study will provide a new route and scientific foundation for establishing green and cheap heterogeneous catalytic process of highly effective hydroxylation of benzene with O2 to phenol.

英文关键词： hydroxylation of benzene to phenol;catalyst design;g-C3N4;heteropoly acids;structure-activity relationship