钯铂纳米材料的表界面调控及其选择性氢化性能研究

Understanding the surface and interface chemical reaction mechanism of nanomaterials at a molecular level can not only achieve precise control of their catalytic performances and reduce the formation of by-products, but also improve the catalytic selectivity, which therefore could be applied to the green chemical production technology. In view of the absence of effective methods in analyzing the surface and interfacial fine structure of nanomaterials, this project puts forward to research the interface chemical processes of nanocatalysts at molecular level. Firstly, load the well-defined copper nanoclusters or organic ligands with amino/sulfhydryl on the two-dimensional palladium/platinum nanomaterials through coordination or charge effect and construct a two-dimensional palladium/platinum nanocatalyst model. Secondly, analyze the microstructure of catalytic active site, then combined with the computational simulations to understand the nature of the related interface chemical processes, construct the active sites on the commercial palladium/platinum nanocatalysts, and finally use them to the selective hydrogenation catalytic system in reality. This project will help us to better understand the structure-activity relationships of catalysts, achieve the effective connection of the basic researches and practical applications, and provide reliable theoretical guidance to the green chemical technology.

在分子水平上认识纳米材料表界面化学反应微观机理是实现其催化性能精准调控、减少副产物形成的重要基础，更是提高催化剂选择性并将其应用于绿色化工生产技术的关键。针对当前缺失在分子尺度上去解析实际纳米材料表界面精细结构的有效手段的现状，本项目提出在分子水平上研究纳米催化材料的界面化学过程，主要内容包括：（1）以二维钯铂纳米材料为基底，结合结构确定的铜的团簇或含氨基、巯基的有机配体，通过电荷作用、配位作用构筑出二维钯铂纳米模型催化剂；（2）从分子水平上解析其催化活性界面基元结构，然后进一步结合计算模拟方法理解相关界面化学过程的本质，并在商业化钯铂纳米催化剂上构筑活性基元，将其应用于实际选择性加氢催化体系。本项目的研究将有助于我们更深入地理解催化剂的构效关系，为实现基础研究与实际应用的有效衔接和形成绿色化工技术提供理论指导。

钯基纳米催化剂在选择性加氢工业中存在重要的应用，在分子水平上认识纳米材料表界面化学反应微观机理，实现其催化性能精准调控、减少副产物形成，可帮助提高催化剂选择性并将其应用于绿色化工生产技术。针对以上思路，本项目主要取得了以下进展：（1）催化材料的设计制备:主要制备了五种催化材料，碳酸钠负载的钯铜纳米枝杈状结构，甲酸保护的钯铜纳米线，双氰胺修饰的钯铜纳米颗粒，银离子辅助组装的铂纳米线以及三元核壳结构的Pd- Sn1.1Nb2O5.5F0.9@SnO2；（2）催化性能的研究：将催化材料用于炔烃选择性氢化的测试及乙烯氧化的测试得到了良好的催化性能；（3）对催化材料进行表征和解析，理论计算解释机理，理解催化剂的构效关系；（4）将催化剂制备方法拓展到商业催化剂并将催化体系拓展，为科研成果转化提供思路。上述研究为工业中的绿色加氢提供了良好的理论依据和技术指导。