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Issue 13, 2017
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Hydrogenation of dimethyl malonate to 1,3-propanediol catalyzed by a Cu/SiO2 catalyst: the reaction network and the effect of Cu+/Cu0 on selectivity

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Abstract

1,3-Propanediol, a vital monomer for the manufacture of commodity polytrimethylene-terephthalate, is commercially produced nowadays through either hydration of acrolein or hydroformylation of ethylene oxide. Herein, for the first time, we present the investigation of an alternative route for 1,3-propanediol production from vapor-phase catalytic hydrogenation of syngas-derived dimethyl malonate on a Cu/SiO2 catalyst. The catalytic reaction network has been disclosed for the Cu/SiO2 catalyst, and the reaction proceeds through sequential hydrogenation with methyl 3-hydroxypropionate as the primary product, which can be further converted into 1,3-propanediol or methyl propionate. Excessive hydrogenation of 1,3-propanediol or methyl propionate leads to the formation of n-propanol. Meanwhile, a small amount of dimethyl malonate cracks into methyl acetate. The structural and textural properties of Cu/SiO2 catalysts with varied copper loadings were extensively characterized by X-ray diffraction, Fourier transform infrared spectroscopy, H2-temperature programmed reduction, X-ray photoelectron spectroscopy, N2 physisorption, CO chemisorption, N2O titration, and transmission electron microscopy. A correlation of the areal activity to copper components suggests that metallic copper modified by the co-present Cu+ species may be the active site for the hydrogenation. The highest 1,3-propanediol selectivity was achieved on a catalyst with a maximum Cu+/(Cu0 + Cu+) ratio of 0.41. The revelation of catalytic networks and insights into the active species can provide guidance for future rational design of catalysts for regioselective hydrogenation of C[double bond, length as m-dash]O bonds in dimethyl malonate.

Graphical abstract: Hydrogenation of dimethyl malonate to 1,3-propanediol catalyzed by a Cu/SiO2 catalyst: the reaction network and the effect of Cu+/Cu0 on selectivity

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Publication details

The article was received on 16 Dec 2016, accepted on 14 Apr 2017 and first published on 17 Apr 2017


Article type: Paper
DOI: 10.1039/C6NJ03960J
Citation: New J. Chem., 2017,41, 5752-5763
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    Hydrogenation of dimethyl malonate to 1,3-propanediol catalyzed by a Cu/SiO2 catalyst: the reaction network and the effect of Cu+/Cu0 on selectivity

    S. Zheng, K. Zhu, W. Li and Y. Ji, New J. Chem., 2017, 41, 5752
    DOI: 10.1039/C6NJ03960J

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