Achieving rhodium-like activity for olefin hydroformylation by electronic metal-support interaction of single atomic cobalt catalyst
Baiyin Wei, Junjun Chen, Xiaofang Liu, Kaimin Hua, Lin Li, Shunan Zhang, Hu Luo, Hui Wang, Yuhan Sun
Abstract
Hydroformylation of olefins with H2 and CO is an important industrial process for aldehyde production, and developing Earth-abundant catalysts with high catalytic activity and stability remains challenging. Here, we synthesize a rhodium-like high-efficiency single-atom cobalt catalyst over β-Mo2C toward olefin hydroformylation. During the hydroformylation of propene, the single atomic cobalt catalyst achieves a turnover number of 3,834 and a turnover frequency of 749 h−1, which to our knowledge surpasses all the reported heterogeneous cobalt-based catalysts and approaches the performance of rhodium catalysts. Moreover, the catalyst can be reused five times without an obvious activity decline, confirming the excellent stability of single-atom Co supported on β-Mo2C. We demonstrate that a Co1-MoxCy motif forms on the carbide surface with electronic metal-support interaction (EMSI). Such an EMSI effect plays a pivotal role in optimizing the charge density, reducing the reaction barrier, and stabilizing the active site.