文献类型：期刊文献

英文题名：Tandem Switch-Triggered On-Demand Synthesis of Aromatic Amines in High Yields

作者：Chen, Zhou[1];Sang, Keng[1];Ye, Lei[1];Zhang, Jian[2];Wang, Xinyue[1];Chen, Wenyao[1];Qian, Gang[1];Zhang, Jing[1];Liu, Jichang[1];Zhou, Xinggui[1];He, Jing[2];Chen, De[3];Yuan, Weikang[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Beijing Univ Chem Technol, State Key Lab Chem Resource Engn, Beijing 100029, Peoples R China;[3]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2025

卷号：64

期号：18

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20251017987349);WOS:【SCI-EXPANDED(收录号:WOS:001436117700001)】；

基金：This work was financially supported by the National Key R&D Program of China (2024YFA1510303), the Natural Science Foundation of China (22478107, 22038003, 22178100, 22178101, and U22B20141), the Shanghai Rising-Star Program (24QA2701900), the Shanghai Pilot Program for Basic Research (22TQ1400100-15), the Innovation Program of Shanghai Municipal Education Commission, the Shanghai Science and Technology Innovation Action Plan (22JC1403800). The authors thank the staff members from the BL11B beamline of Shanghai Synchrotron Radiation Facility (SSRF) for assistance during data collection.

语种：英文

外文关键词：tandem switch; on-demand synthesis; aromatic amines; site and component incompatibilities; reaction mechanism

摘要：Tandem catalysis stands as a beacon of chemical sustainability. Although bifunctional catalysts have achieved wide success in two-step tandem reactions, achieving multi-step catalysis with three or more distinct and potentially incompatible catalytic sites and components remains an ambitious challenge. Here, we present a "tandem switch" strategy that transforms these incompatibilities into functional advantages, enabling on-demand production of primary, secondary, and tertiary aromatic amines, all with yields exceeding 96 %. A kinetic switch, enabled by phosphotungstic acid functionalization of the Ni-Ni(Al)O heterojunction catalyst, modulates the Ni-Ni and Ni-O boundary microenvironment to simultaneously accelerate the rate-determining steps in nitrobenzene hydrogenation, N-alkylation, and aza-Michael addition. Meanwhile, a thermodynamic switch, controlled by the competitive adsorption of ethanol, hydrogen, and acrylonitrile, stepwise minimizes Gibbs free energy to ensure a seamless reaction cascade. Hence, by toggling these tandem switches on or off, we achieve selective regulation of nitrobenzene conversion pathways into the production of targeted aromatic amine. Techno-economic analysis shows the developed process significantly reduces material and energy consumption for sustainable amine production.