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二氧化铈的晶面效应在不饱和醛液相加氢负载型铜催化剂中的应用

Crystal plane effect of ceria on supported copper catalyst for liquid-phase hydrogenation of unsaturated aldehyde.

作者信息

Hu Zhi, Zou Zidan, Xie Aidi, Chen Chun, Zhu Xiaoguang, Zhang Yunxia, Zhang Haimin, Zhao Huijun, Wang Guozhong

机构信息

Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Key Laboratory of Materials Physics, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, China; Science Island Branch of Graduate School, University of Science and Technology of China, Hefei 230026, China.

University of Science and Technology of China, Hefei 230026, China.

出版信息

J Colloid Interface Sci. 2021 Aug 15;596:34-43. doi: 10.1016/j.jcis.2021.03.137. Epub 2021 Mar 27.

Abstract

Ceria has been widely used as catalyst support displaying a size- or shape-dependent catalytic performance due to the strong metal-support interaction (SMSI) effect with active metal. Almost all the studies on the SMSI effect of ceria-supported metal catalysts are involved generally in gas-phase reaction, but rarely in the liquid-phase reaction system. In this work, Cu/CeO-P (copper loaded on nano-polyhedral CeO with (111) terminated surface) was investigated its catalytic performance on liquid-phase hydrogenation and studied the SMSI effect by comparing with the catalysts supported on nano-rod and nano-cube CeO. It was found that Cu was highly dispersed on the external surface of ceria in the Cu/CeO-P catalyst via a moderate SMSI effect. Furthermore, the degree of the interaction showed great influence on the chemical state of Cu species, and the ratio of (Cu+Cu)/Cu in Cu/CeO-P was higher than Cu/CeO-R (Cu loaded on nano-rod CeO with (110) plane) and Cu/CeO-C (Cu loaded on nano-cube CeO with (100) facet). As a result, the Cu/CeO-P catalyst showed the best catalytic performance among three types of catalysts. Based on series of catalytic investigations, the catalytic performance in liquid-phase hydrogenation was intrinsically relevant to the crystal plane effect and reduced Cu proportion induced by an appropriate SMSI effect, which was completely different from gas-phase hydrogenation.

摘要

二氧化铈作为催化剂载体已被广泛应用,由于其与活性金属之间存在强金属-载体相互作用(SMSI)效应,因而表现出尺寸或形状依赖性的催化性能。几乎所有关于二氧化铈负载金属催化剂SMSI效应的研究通常都涉及气相反应,而在液相反应体系中却很少见。在本工作中,研究了Cu/CeO-P(负载在具有(111)终止表面的纳米多面体CeO上的铜)在液相加氢反应中的催化性能,并通过与负载在纳米棒和纳米立方体CeO上的催化剂进行比较来研究SMSI效应。结果发现,通过适度的SMSI效应,Cu在Cu/CeO-P催化剂中高度分散在二氧化铈的外表面。此外,相互作用的程度对Cu物种的化学状态有很大影响,且Cu/CeO-P中(Cu⁺+Cu)/Cu的比例高于Cu/CeO-R(负载在具有(110)面的纳米棒CeO上的铜)和Cu/CeO-C(负载在具有(100)面的纳米立方体CeO上的铜)。因此,Cu/CeO-P催化剂在三种催化剂中表现出最佳的催化性能。基于一系列催化研究,液相加氢反应中的催化性能本质上与晶面效应以及由适当的SMSI效应诱导的还原态Cu比例相关,这与气相加氢完全不同。

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