Tuning the regioselectivity of heterogeneous hydroformylation by engineering carbon species microenvironment around Rh sites

IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Journal of Catalysis Pub Date : 2025-03-23 DOI:10.1016/j.jcat.2025.116095
Li Huang , Jia Wang , Qi Liu , Peng Sun , Mengnan Nie , Guang Gao , Zelun Zhao , Zhiwei Huang , Fuwei Li
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Abstract

Olefin hydroformylation is one of the most important industrial processes for aldehyde synthesis. Heterogeneous catalysts are easy to separate compared with homogeneous catalysts, yet with limited success in activity and regioselectivity control. In the present work, a zeolite-encapsulated rhodium carbide species (RhCx@S-1) catalyst was developed, demonstrating not only relatively high catalytic activity but also good regioselectivity and stability in heterogeneous hydroformylation. The unique microenvironment of rhodium carbide species was formed in situ during the catalyst carbonization reduction process, tuning the steric and electronic characteristics of Rh species to obtain more linear aldehydes. This work shows an alternative strategy to promote the regioselectivity of olefin hydroformylation catalyzed by zeolite-confined catalysts and provides insights into the selective regulation of heterogeneous catalysts.

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通过在Rh位点周围设计碳种微环境来调节非均相氢甲酰化的区域选择性
烯烃氢甲酰化反应是醛合成最重要的工业工艺之一。与均相催化剂相比,非均相催化剂易于分离,但在活性和区域选择性控制方面的成功程度有限。本文研制了一种沸石包封的碳化铑催化剂(RhCx@S-1),该催化剂在丙烯非均相氢甲酰化反应中不仅具有较高的催化活性,而且具有良好的区域选择性和稳定性。在催化剂碳化还原过程中,原位形成了独特的碳化铑微环境,调整了铑的位阻和电子特性,得到了更多的线性醛。这项工作显示了一种促进沸石限制催化剂催化烯烃氢甲酰化区域选择性的替代策略,并为非均相催化剂的选择性调节提供了见解。
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来源期刊
Journal of Catalysis
Journal of Catalysis 工程技术-工程:化工
CiteScore
12.30
自引率
5.50%
发文量
447
审稿时长
31 days
期刊介绍: The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.
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