非贵金属Cu-N-C纳米杂化结构催化剂构建与结构调控以及在炔烃偶联反应构效关系研究

开发高效高稳定性非贵金属催化剂，是实现精细化学品“绿色可持续”生产的关键。本项目以新型非贵金属Cu-N-C纳米杂化结构催化剂的创制为研究对象，提出以可再生生物质为C/N源高温热解法和非接触高温热解法构建单原子分散Cu-N-C催化剂及结构调控机制为主要研究目标，重点围绕(1)高温热解过程中生物质基碳材料高密度原子分散Cu-Nx活性位点的形成机制；（2）Cu-N-C活性位点微观结构的可控调变和化学原理；以及（3）微观结构与末端炔烃活化偶联反应性能的构效关系等3个关键科学问题，解决现有方法制备M-N-C催化剂中（1）存在混合金属物相，降低金属原子利用率，增加明确真正活性位点难度；（2）金属负载量低；及（3）合成原料昂贵、过程繁琐等问题，为开发高性能高密度单原子分散M-N-C纳米结构催化剂提供新的思路和理论，同时为绿色高效合成1,3-二炔和1,2,3-三唑类化合物等重要精细化学品提供新路线。

The development of non-noble metal catalysts with high activity and stability is the key for the synthesis of fine chemicals in a green and sustainable manner, but still remains a great challenge. In this project, the research will be focused on the fabrication of novel non-noble metal nanostructured Cu-N-C catalysts with high-density of single-atom active sites. The current synthetic strategies for fabricating M-N-C catalysts via high-temperature pyrolysis unavoidably led to a structural heterogeneity with the presence of a mixture of species including atomically dispersed M-Nx moieties (commonly regarded as active sites) and inorganic metal-containing particles, which minimize the atomic utilization and cloud the accurate understanding of the nature of the catalytically active sites. In addition, to accomplish the highly dense atomic dispersion of M-Nx sites, post-treatment with harsh conditions are frequently employed to remove the anti-washing or acid-resistant metal-containing particles, which once again caused other issues such as introduction of new functional groups, damage of the structure of active sites, or rearrangement of carbon skeletons. To solve these issues, we propose a new straightforward and cost-effective preparation strategy for constructing atomically dispersed Cu-Nx moieties on biomass-derived N-doped porous carbon without formation any insoluble metal-containing particles, in which high temperature pyrolysis and non-contact pyrolysis strategies will be employed using naturally renewable and easily available biomass as C and N sources together with inexpensive and non-toxic copper salts. Intensive studies will be performed (1) to unveil the formation mechanism of single-atom Cu-Nx on N-doped carbon via pyrolysis; (2) to rationalize how to precisely tune the microenvironment of the catalytically active sites and to get a better understanding of the principle; (3) to establish the relationship between microenvironment of active sites and catalytic activity for terminal alkyne coupling reactions. We expect that this study will not only open up a fancy pathway in the rational design and preparation of novel atomically dispersed M-N-C with high-density of active sites and excellent activity and stability as well, but also will offer an innovative synthetic route for accessing industrially versatile and important fine chemicals 1,3-diynes and 1,2,3-triazoles in a highly efficient and sustainable fashion.