Mo 2 C Morphology Dependence in Co–Mo 2 C Interface Structure Evaluation for Boosting α-Olefin Hydroformylation

作者：Zhuo Li, Huimin Yang, Rui Gao, Peng He, Xingchen Liu, Ruilin Liu, Xiaomin Dai, Yunhua Xu, Yong Qin, Bin Zhang · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c05686 · 被引用次数：1 · 研究领域：Catalysis and Hydrodesulfurization Studies、Catalysts for Methane Reforming、Organometallic Complex Synthesis and Catalysis

The hydroformylation of high-carbon α-olefins is a pivotal industrial process. Still, heterogeneous Co-based catalysts suffer from low activity and Co leaching due to strong coordination of CO to Co atoms. Herein, we address the dynamic evolution and active structure of Co species by interacting Co nanoparticles or ultrahigh-dispersed clusters with β-Mo 2 C nanoparticles (Co-30Mo 2 C particle /CNF) and nanofilms (Co-100Mo 2 C film /CNF) on carbon nanofibers. The specific activity in the formation of heptanal from 1-hexene hydroformylation increased by 10.7 times on Co-30Mo 2 C particle /CNF (21.4 mol heptanal /mol Co /h) and 2.4 times on Co-100Mo 2 C film /CNF (4.7 mol heptanal /mol Co /h) compared with Co/CNF (2.0 mol heptanal /mol Co /h). Moreover, Co-100Mo 2 C film /CNF exhibits enhanced stability with only 1.7% Co leaching. The Mo 2 C nanoparticles interact with Co nanoparticles, oxidizing them to form highly active Co-MoO x sites with a lower CO insertion barrier. The reaction environment influences the structural evolution of the Co-MoO x interaction. In contrast, Mo 2 C nanofilms form robust Co–C and Co–Mo bonds at the Co–Mo 2 C interface, stabilizing atomically distributed Co clusters against leaching. This work establishes a morphology-driven strategy to control the dynamic interaction of Co and additives, thereby decoupling activity and stability in heterogeneous catalysis for hydroformylation.