M-N/C型材料的设计、制备及催化加氢性能研究

Catalytic hydrogenation is one of the most important green method of reduction in the manufacturing of fine chemicals. However, metallic support catalysts applied in this method not only exist many shortages, such as rapid loss of activity and poor tolerance, but also may cause the risk of heavy metal pollution. In recent years, M-N/C materials, which are synthesized from pyrolysis of the complexes based on metal ions and N-containing organic ligands, have attracted much attention due to their superior characteristics of economy, environment protection, and high activity. Unfortunately, many critical issues of M-N/C catalysts, such as active sites and catalytic mechanism, are still leaved over. These problems lead to the limitation of applying M-N/C catalysts in chemical reactions, which have severely restricted their development. In this project, design, synthesis, and catalytic hydrogenation activity of M-N/C materials will be studied in particular. By the studies of structure-activity relationship, the effects of different components in M-N/C materials and the hydrogenation activity site will be confirmed. Moreover, M-N/C catalysts will be applied in the reductive cyclization that constructs the benzotriazole ring, and a clean synthesis method of benzotriazoles will be established. Meanwhile, the reaction mechanism of reductive cyclization will be explored to provide theoretical foundation for the development of subsequent preparation technics. This project may serve as a theoretical underpinning for future research and practical applications of M-N/C materials. Not only that, the results of this research will promote the progress of related research areas and green development of light stabilizer industry.

在精细化学品制造业中，催化加氢是一种重要的绿色还原方法，但其普遍使用的金属负载型催化剂一直存在易失活、耐受性差、重金属污染等问题和隐患。近年来，人们通过热解金属与含氮配体形成的配合物制得了新型M-N/C材料，因其经济、环保、活性高等优点而备受科学家们青睐。但由于该类催化材料的活性位点及催化机制等关键问题尚不明确，仅见报道应用于部分简单的化学反应，严重制约了其发展。本项目主要设计、制备M-N/C型材料并研究其催化加氢性能。通过构效关系研究，考察催化剂中各组分所发挥的作用，明确催化加氢活性位点。此外，本项目计划将M-N/C型催化材料应用于苯并三唑母环结构的构筑，建立一种苯并三唑类化合物的清洁合成方法，同时对相关还原环化反应机理进行探索。通过本项目的研究，能够为后续此类催化材料的研究工作提供理论基础，推动相关研究领域的进步，并有望促进光稳定剂制造业的绿色发展。

氢能源是公认的清洁能源，催化加氢是经济环保的还原技术，广泛应用于有机合成与精细化工领域。M-N/C型催化材料因金属利用率高、稳定性好等诸多优势能有效解决传统加氢催化剂存在的问题，一经报道便引起广泛关注。本项目旨在解决M-N/C型催化材料活性位点及催化机制不明确、活性不易调控导致其应用受限等问题。首先，明确了该类催化材料的加氢活性位点是高温条件下构筑的M-N位点。同时深入研究了催化机制，发现M-N位点活化氢气分子的机理类似于受阻Lewis酸碱对。其中金属纳米颗粒与氮物种之间由于存在较弱的相互作用而形成“活性区域”，可异裂活化氢分子。此外，利用“糖衣”包裹、MOFs前体及固溶体三种策略成功构筑了高分散M-N/C型催化材料。打破了高温条件对其活性可控化制备的限制，大幅度提升了材料的催化活性，拓宽了应用范围。将筛选的M-N/C型催化材料应用于苯并三唑类化合物等精细化工产品的制备，建立了相关的清洁制造工艺。本项目为M-N/C型催化材料的发展奠定了理论及实验基础，为相关催化材料的设计与制备提供了新思路，同时促进了精细化工制造业的绿色发展。