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铜的初始氧化态对草酸二甲酯催化加氢制乙二醇的重要性

Importance of the Initial Oxidation State of Copper for the Catalytic Hydrogenation of Dimethyl Oxalate to Ethylene Glycol.

作者信息

Sun Yannan, Meng Fanqiong, Ge Qingjie, Sun Jian

机构信息

Dalian National Laboratory for Clean Energy Dalian Institute of Chemical Physics, Chinese Academy of Sciences 457 Zhongshan Road Dalian 116023 China.

School of Chemical Engineering University of Chinese Academy of Sciences 380 Huaibeizhuang, Huaibei Town, Huairou District Beijing 101408 China.

出版信息

ChemistryOpen. 2018 Nov 20;7(12):969-976. doi: 10.1002/open.201800225. eCollection 2018 Dec.

Abstract

Exposing a Cu-based catalyst to a suitable temperature is of great importance to optimize its hydrogenation performance, as copper is sensitive to temperature. Herein, we investigated the effect of the initial oxidation state of copper, tuned by the reduction temperature, on its catalytic performance in the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG) through designing a series of catalysts with different reduction temperatures (200-350 °C). Among these catalysts, the Cu/SiO catalyst prepared by ammonia evaporation with a hydrogen reduction process at 250 °C showed the best performance in the hydrogenation of DMO with a conversion of 100 % and a selectivity to EG higher than 95 %. The relationship between the initial oxidation state of copper and catalytic performance was well established by characterizing the physicochemical properties of the Cu/SiO catalysts by XRD, TEM, H temperature-programmed reduction, NO adsorption, and in situ reduction Auger electron spectroscopy. The initial oxidation state of copper determined the conversion of DMO and the distribution of the products, and it could be balanced by reducing the temperature to improve the activity of the catalyst. This work provides a reference for further exploration of the mechanism and guidance for the design of catalysts for the hydrogenation of esters.

摘要

由于铜对温度敏感,将铜基催化剂暴露在合适的温度下对于优化其氢化性能至关重要。在此,我们通过设计一系列具有不同还原温度(200 - 350°C)的催化剂,研究了通过还原温度调节的铜的初始氧化态对其在草酸二甲酯(DMO)加氢制乙二醇(EG)反应中的催化性能的影响。在这些催化剂中,通过氨蒸发法制备并在250°C下进行氢气还原过程得到的Cu/SiO催化剂在DMO加氢反应中表现出最佳性能,DMO转化率达到100%,对EG的选择性高于95%。通过XRD、TEM、H程序升温还原、NO吸附和原位还原俄歇电子能谱对Cu/SiO催化剂的物理化学性质进行表征,很好地建立了铜的初始氧化态与催化性能之间的关系。铜的初始氧化态决定了DMO的转化率和产物分布,通过降低温度可以平衡这种关系以提高催化剂的活性。这项工作为进一步探索酯加氢反应的机理提供了参考,并为酯加氢催化剂的设计提供了指导。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d10b/6276878/f3906fcfea6f/OPEN-7-969-g001.jpg

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