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理解碱物种在呋喃化合物开环生成1,2-戊二醇的反相铜催化剂中的作用。

Understanding the Role of Base Species on Reversed Cu Catalyst in Ring Opening of Furan Compounds to 1, 2-Pentanediol.

作者信息

Li Huixiang, Nie Xuezhong, Du Hong, Zhao Yang, Mu Junju, Zhang Z Conrad

机构信息

National-local Joint Engineering Research Center of Biomass Refining and High-quality Utilization, Changzhou University, Changzhou, 213164, China.

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

出版信息

ChemSusChem. 2024 Jan 8;17(1):e202300880. doi: 10.1002/cssc.202300880. Epub 2023 Oct 30.

DOI:10.1002/cssc.202300880
PMID:37697441
Abstract

The hydrogenation of biomass-derived furan compounds provides a sustainable pathway for the production of various valuable chemicals; product selectivity among multiple reaction pathways of furan compound hydrogenation is crucially dependent on catalytic sites; however controlling reaction pathways remains challenging due to the lack of identification and understanding of active sites. In this work we reveal the role of base sites in furfural selective hydrogenation through deliberately designed and synthesized reversed catalysts, basic metal oxides and hydroxide on Cu. It is demonstrated that base species greatly enhanced the selectivity of 1, 2-pentanediol (1, 2-PeD) from furfural, presenting a nearly fourfold increase of 1, 2-PeD: methyl furan ratio over the Cu based reverse catalysts. A combination of infrared spectroscopy and DFT calculations demonstrates the strong interaction between the C-O-C bond in furan ring and the catalyst surface in preferentially parallel adsorption mode in the presence of base species on Cu, thus facilitating the activation of C-O-C bond to produce 1, 2-PeD. This work provides a strategy of designing reversed catalyst to study the effect of promoters and reveals the role of base sites in the hydrogenation of biomass-derived furan compounds to diols.

摘要

生物质衍生呋喃化合物的加氢反应为各种有价值化学品的生产提供了一条可持续途径;呋喃化合物加氢的多个反应途径之间的产物选择性关键取决于催化位点;然而,由于缺乏对活性位点的识别和理解,控制反应途径仍然具有挑战性。在这项工作中,我们通过精心设计和合成的反向催化剂(负载在铜上的碱性金属氧化物和氢氧化物)揭示了碱性位点在糠醛选择性加氢中的作用。结果表明,碱性物种极大地提高了糠醛制1,2 - 戊二醇(1,2 - PeD)的选择性,与基于铜的反向催化剂相比,1,2 - PeD与甲基呋喃的比例提高了近四倍。红外光谱和密度泛函理论计算相结合表明,在铜表面存在碱性物种的情况下,呋喃环中的C - O - C键与催化剂表面以优先平行吸附模式存在强相互作用,从而促进C - O - C键的活化以生成1,2 - PeD。这项工作提供了一种设计反向催化剂以研究助剂作用的策略,并揭示了碱性位点在生物质衍生呋喃化合物加氢制二醇反应中的作用。

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