Regioselective hydroformylation of propene catalysed by rhodium-zeolite

• 成果类型: Article
• 署名作者: Zhang, Xiangjie; Yan, Tao; Hou, Huaming; Yin, Junqing; Wan, Hongliu; Sun, Xiaodong; Zhang, Qing; Sun, Fanfei; Wei, Yao; Dong, Mei; Fan, Weibin; Wang, Jianguo; Sun, Yujie; Zhou, Xiong; Wu, Kai; Yang, Yong; Li, Yongwang; Cao, Zhi
• 署名单位: Chinese Academy of Sciences; Institute of Coal Chemistry, CAS; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; Chengdu University; ShanghaiTech University; Chinese Academy of Sciences; Shanghai Advanced Research Institute, CAS; University System of Ohio; University of Cincinnati; Chinese Academy of Sciences; Peking University
• 刊物名称: Nature
• ISSN/ISSBN: 0028-6848
• DOI: 10.1038/s41586-024-07342-y
• 发表日期: 2024-05-16
• 页码: 597-+
• 关键词: fixed-bed hydroformylation; finding saddle-points; elastic band method; metal-clusters; oxidation; rh; approximation; STABILITY; reduction; insights

摘要

Hydroformylation is an industrial process for the production of aldehydes from alkenes(1,2). Regioselective hydroformylation of propene to high-value n-butanal is particularly important, owing to a wide range of bulk applications of n-butanal in the manufacture of various necessities in human daily life(3). Supported rhodium (Rh) hydroformylation catalysts, which often excel in catalyst recyclability, ease of separation and adaptability for continuous-flow processes, have been greatly exploited(4). Nonetheless, they usually consist of rotationally flexible and sterically unconstrained Rh hydride dicarbonyl centres, only affording limited regioselectivity to n-butanal(5-8). Here we show that proper encapsulation of Rh species comprising Rh(I)-gem-dicarbonyl centres within a MEL zeolite framework allows the breaking of the above model. The optimized catalyst exhibits more than 99% regioselectivity to n-butanal and more than 99% selectivity to aldehydes at a product formation turnover frequency (TOF) of 6,500h(-1), surpassing the performance of all heterogeneous and most homogeneous catalysts developed so far. Our comprehensive studies show that the zeolite framework can act as a scaffold to steer the reaction pathway of the intermediates confined in the space between the zeolite framework and Rh centres towards the exclusive formation of n-butanal.