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负载于碳纳米管上的尺寸依赖性铜纳米颗粒,具有平衡的Cu和Cu双位点用于碳酸亚乙酯的选择性加氢

Size-Dependent Copper Nanoparticles Supported on Carbon Nanotubes with Balanced Cu and Cu Dual Sites for the Selective Hydrogenation of Ethylene Carbonate.

作者信息

Li Huabo, Ji Deyuan, Zhang Yanfei, Cui Yuanyuan, Cheng Yinfeng, Wang Songlin, Dai Wei-Lin

机构信息

School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang, 453003, Henan Province, P. R. China.

Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.

出版信息

Chemistry. 2024 Dec 18;30(71):e202402699. doi: 10.1002/chem.202402699. Epub 2024 Nov 12.

DOI:10.1002/chem.202402699
PMID:39354575
Abstract

Cyclic carbonate hydrogenation offers an alternative for the efficient indirect CO utilization. In this study, a series of carbon nanotubes (CNTs) supported xCu/CNTs catalysts with different Cu loadings were fabricated using a convenient impregnation method, and exhibited excellent catalytic activity for the hydrogenation of ethylene carbonate to methanol and ethylene glycol. The structural and physicochemical properties revealed that acid treatment of CNTs resulted in plentiful oxygen-containing functional groups, providing sufficient anchoring sites for copper species. The calcination process conducted under an inert atmosphere resulted in the formation of ternary CuO, CuO, and Cu composites, enhancing the metal-support interaction and facilitating the formation of balanced Cu and Cu dual sites as well as high active surface area after reduction. Contributed to the synergetic effect of balanced Cu and Cu species proved by density functional theory calculation and the electron-rich CNTs surface, the 40Cu/CNTs catalyst achieved strengthened catalytic performance with methanol yield of 83 %, ethylene glycol yield of 99 % at ethylene carbonate conversion of >99 %, and 150 h of long-term running stability. Consequently, CNTs supported Cu serve as efficient non-silica based catalyst for ester hydrogenation.

摘要

环状碳酸酯加氢为高效间接利用CO提供了一种替代方法。在本研究中,采用简便的浸渍法制备了一系列具有不同铜负载量的碳纳米管(CNTs)负载的xCu/CNTs催化剂,这些催化剂对碳酸乙烯酯加氢制甲醇和乙二醇表现出优异的催化活性。结构和物理化学性质表明,对CNTs进行酸处理会产生大量含氧官能团,为铜物种提供了足够的锚固位点。在惰性气氛下进行的煅烧过程导致形成三元CuO、CuO和Cu复合材料,增强了金属-载体相互作用,并促进了平衡的Cu和Cu双位点的形成以及还原后高活性表面积的形成。得益于密度泛函理论计算证明的平衡Cu和Cu物种的协同效应以及富含电子的CNTs表面,40Cu/CNTs催化剂实现了增强的催化性能,在碳酸乙烯酯转化率>99%时,甲醇产率为83%,乙二醇产率为99%,并具有150小时的长期运行稳定性。因此,CNTs负载的Cu作为酯加氢的高效非硅基催化剂。

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