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Promoted Hydroformylation of Formaldehyde By Electronic Metal–Support Interactions in N-Group Functionalized Silica Supported Rhodium Catalyst

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Abstract

The influence of surface modification of SiO2 carrier by grafting method and its effects for Rh supporting was investigated on formaldehyde hydroformylation reaction. The relationship between the structure of catalysts and their performance was characterized in detail by X-ray diffraction, N2 adsorption–desorption, temperature programmed reduction with H2, X-ray photoelectron spectroscopy, and in situ infrared. After grafting the amino organic functional group, the surface circumstance of SiO2 was altered, and moreover, sites available for metal loading was enriched on the carrier that distribute a high dispersion of Rh species Under the same Rh loading, the Rh@N–SiO2 catalyst exhibits better catalytic activity than pristine SiO2 supported Rh catalysts. Spectroscopic evidences suggest the presence of an electronic perturbation between Rh and modified SiO2 which promotes the hydroformylation of formaldehyde by maintaining Rh at proper Rh0/(Rh3+ + Rhδ+) ratio.

Graphic Abstract

Diagram of the effect of surface modified with amino group on metal rhodium loading.

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Acknowledgements

This work was supported by National Key R&D Program of China (2017YFB0307301, 2017YFA0206802, 2018YFA0704502), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21020800), the Science and Technology Service Network Initiative (KFJ-STS-QYZD-048), the NSF of China (21703247), the Science Foundation of Fujian Province (2018J05029, 2019J05156, 2019H0053) and Guizhou Province ([2018]2193, 2020-1-10).

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Authors and Affiliations

  1. Key Laboratory of Coal-to-Ethylene Glycol and Related Technologies of the Chinese Academy of Sciences, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, People’s Republic of China

    Jie Chen, Luyang Qiao, Zhangfeng Zhou, Xiaoman Wu, Xiaxin Guo, Shanshan Zong, Yifan Ding, Yuntao He & Yuangen Yao

  2. University of Chinese Academy of Science, Beijing, 100049, People’s Republic of China

    Jie Chen

  3. College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 35007, People’s Republic of China

    Xiaxin Guo

  4. College of Chemistry, Fuzhou University, Fuzhou, 350116, People’s Republic of China

    Yifan Ding & Yuntao He

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  1. Jie Chen
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Chen, J., Qiao, L., Zhou, Z. et al. Promoted Hydroformylation of Formaldehyde By Electronic Metal–Support Interactions in N-Group Functionalized Silica Supported Rhodium Catalyst. Catal Lett 151, 3664–3674 (2021). https://doi.org/10.1007/s10562-021-03568-x

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