基于Brønsted固体酸本征质子导向吸附及质子化作用构筑高选择性催化剂并应用于硝基苯乙烯类衍生物还原反应

取代硝基苯乙烯化合物水媒介异质催化还原反应是制备苯胺系列衍生物的绿色、安全方案,但是-NO2官能团选择还原和催化剂长效稳定是阻碍其工业化应用的技术瓶颈。本项目选择耐酸、耐碱、高稳定的质子嵌入式钽酸盐固体酸为催化剂载体，拟合纳米金属或金属氧化物，制备系列硝基芳烃还原催化剂M/ R2-xHxTa2O6 (M= Ag，Cu， CuO等；R=H，Li，Na，K，Rb，Cs等)，设计制备出还原硝基苯乙烯高活性、高选择性和持久稳定性的催化剂，促进该反应的工业化应用；同时通过追踪固体酸载体活性中心（本征质子H）迁移和反应路径以及模拟催化剂多级层层表面的金属沉积模式及质子迁移通道，系统深入探索本征质子的导向吸附以及质子化作用，获得结构内质子H参与并显著提高催化反应活性和选择性的机制以及对催化剂长效性发挥的作用，为新型催化剂的构建提供有价值的设计思路，拓展钽酸盐固体酸在多种H-迁移还原反应中的应用。

The heterogeneous catalytic reduction of the substituted nitrostyrene compounds in aqueous media is a green and safe strategy for the preparation of aniline series derivatives. However, selective reduction of -NO2 functional groups and long-term stability of catalysts in the case of the reactants with several reducible groups are technical difficulties and thus significantly hinder their industrial application. In this project, by fitting the selected metal or metal oxides into the various proton-embedded tantalate solid acid support with acid-resistant and alkali-resistant, a series of catalysts M/R2-xHxTa2O6)(M=Au, Ag, Cu, Ni, Co; M= H, Li, Na, K, Rb, Cs) for nitroarene reduction were prepared. By tracking the migration and reaction path of the active center from solid acid support (H proton), as well as simulating invesiting the metal deposition pattern and proton migration channel in the multilayer surface of catalyst, we will invesitigate the steered adsorption and protonation, achieve the mechanism involved in and significantly improved the catalytic activity and selectivity, as well as understanding the role in the reusability of catalyst for these structural proton H soecies from the solid acid center. Fourthmore, we will design to prepare the catalyst with high activity, high selectivity and lasting stability for nitroethylene styrene with multi-functional groups, and to promote the industrial application for heterogeneous catalytic reaction of nitrostyrene. Also, the application of solid Brønsted acid will be expanded in various hydrogen transfer catalytic reactions and a valuable design idea could be provided to construct novel catalysts (and/or supports) for these H-transport reduction reactions.