Impact of the Cu2O microcrystal planes on active phase formation in the Rochow reaction and an experimental and theoretical understanding of the reaction mechanism

Jing Li; Li Li Yin; Yongjun Ji; Hezhi Liu; Yu Zhang; Xue Qing Gong; Ziyi Zhong; Fabing Su

doi:10.1016/j.jcat.2018.02.010

Impact of the Cu₂O microcrystal planes on active phase formation in the Rochow reaction and an experimental and theoretical understanding of the reaction mechanism

Jing Li, Li Li Yin, Yongjun Ji^*, Hezhi Liu, Yu Zhang, Xue Qing Gong, Ziyi Zhong, Fabing Su

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

Abstract

In heterogeneous catalysis, on one hand, people always want to know about reaction details, such as what the most active phase is, how it is formed, and what is the reaction mechanism. On the other hand, it is still very challenging to probe these reaction details, particularly at high reaction temperatures and pressures. Here, we report the microcrystal plane-controlled catalytic performance on well-defined Cu₂O cube, octahedron, and rhombic-dodecahedron catalysts in the Rochow reaction. It was found that the Cu₂O cube exposing {1 0 0} crystal planes gave the highest dimethyldichlorosilane selectivity and yield, while the Cu₂O rhombic-dodecahedron exposing {1 1 0} crystal planes showed the lowest selectivity and yield. Our experimental observation, as well as density functional theory calculations, demonstrated that the enhanced selectivity and yield stemmed from the stronger dissociative adsorption of methyl chloride on the Cu₂O{1 0 0} plane, which greatly promoted the transformation of Cu₂O into Cu₃Si active phases under the reaction conditions. This work reveals a new strategy for controlling the surface structure of catalysts in order to enhance their catalytic performance.

Original language	English
Pages (from-to)	73-83
Number of pages	11
Journal	Journal of Catalysis
Volume	361
DOIs	https://doi.org/10.1016/j.jcat.2018.02.010
State	Published - May 2018
Externally published	Yes

Keywords

Catalytic performance
Crystal plane
CuO microcrystals
Heterogeneous catalysis
Rochow reaction

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10.1016/j.jcat.2018.02.010

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title = "Impact of the Cu2O microcrystal planes on active phase formation in the Rochow reaction and an experimental and theoretical understanding of the reaction mechanism",

abstract = "In heterogeneous catalysis, on one hand, people always want to know about reaction details, such as what the most active phase is, how it is formed, and what is the reaction mechanism. On the other hand, it is still very challenging to probe these reaction details, particularly at high reaction temperatures and pressures. Here, we report the microcrystal plane-controlled catalytic performance on well-defined Cu2O cube, octahedron, and rhombic-dodecahedron catalysts in the Rochow reaction. It was found that the Cu2O cube exposing {1 0 0} crystal planes gave the highest dimethyldichlorosilane selectivity and yield, while the Cu2O rhombic-dodecahedron exposing {1 1 0} crystal planes showed the lowest selectivity and yield. Our experimental observation, as well as density functional theory calculations, demonstrated that the enhanced selectivity and yield stemmed from the stronger dissociative adsorption of methyl chloride on the Cu2O{1 0 0} plane, which greatly promoted the transformation of Cu2O into Cu3Si active phases under the reaction conditions. This work reveals a new strategy for controlling the surface structure of catalysts in order to enhance their catalytic performance.",

keywords = "Catalytic performance, Crystal plane, CuO microcrystals, Heterogeneous catalysis, Rochow reaction",

author = "Jing Li and Yin, {Li Li} and Yongjun Ji and Hezhi Liu and Yu Zhang and Gong, {Xue Qing} and Ziyi Zhong and Fabing Su",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier Inc.",

year = "2018",

month = may,

doi = "10.1016/j.jcat.2018.02.010",

language = "英语",

volume = "361",

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journal = "Journal of Catalysis",

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T1 - Impact of the Cu2O microcrystal planes on active phase formation in the Rochow reaction and an experimental and theoretical understanding of the reaction mechanism

AU - Li, Jing

AU - Yin, Li Li

AU - Ji, Yongjun

AU - Liu, Hezhi

AU - Zhang, Yu

AU - Gong, Xue Qing

AU - Zhong, Ziyi

AU - Su, Fabing

PY - 2018/5

Y1 - 2018/5

N2 - In heterogeneous catalysis, on one hand, people always want to know about reaction details, such as what the most active phase is, how it is formed, and what is the reaction mechanism. On the other hand, it is still very challenging to probe these reaction details, particularly at high reaction temperatures and pressures. Here, we report the microcrystal plane-controlled catalytic performance on well-defined Cu2O cube, octahedron, and rhombic-dodecahedron catalysts in the Rochow reaction. It was found that the Cu2O cube exposing {1 0 0} crystal planes gave the highest dimethyldichlorosilane selectivity and yield, while the Cu2O rhombic-dodecahedron exposing {1 1 0} crystal planes showed the lowest selectivity and yield. Our experimental observation, as well as density functional theory calculations, demonstrated that the enhanced selectivity and yield stemmed from the stronger dissociative adsorption of methyl chloride on the Cu2O{1 0 0} plane, which greatly promoted the transformation of Cu2O into Cu3Si active phases under the reaction conditions. This work reveals a new strategy for controlling the surface structure of catalysts in order to enhance their catalytic performance.

AB - In heterogeneous catalysis, on one hand, people always want to know about reaction details, such as what the most active phase is, how it is formed, and what is the reaction mechanism. On the other hand, it is still very challenging to probe these reaction details, particularly at high reaction temperatures and pressures. Here, we report the microcrystal plane-controlled catalytic performance on well-defined Cu2O cube, octahedron, and rhombic-dodecahedron catalysts in the Rochow reaction. It was found that the Cu2O cube exposing {1 0 0} crystal planes gave the highest dimethyldichlorosilane selectivity and yield, while the Cu2O rhombic-dodecahedron exposing {1 1 0} crystal planes showed the lowest selectivity and yield. Our experimental observation, as well as density functional theory calculations, demonstrated that the enhanced selectivity and yield stemmed from the stronger dissociative adsorption of methyl chloride on the Cu2O{1 0 0} plane, which greatly promoted the transformation of Cu2O into Cu3Si active phases under the reaction conditions. This work reveals a new strategy for controlling the surface structure of catalysts in order to enhance their catalytic performance.

KW - Catalytic performance

KW - Crystal plane

KW - CuO microcrystals

KW - Heterogeneous catalysis

KW - Rochow reaction

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DO - 10.1016/j.jcat.2018.02.010

M3 - 文章

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SN - 0021-9517

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JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Impact of the Cu₂O microcrystal planes on active phase formation in the Rochow reaction and an experimental and theoretical understanding of the reaction mechanism

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Keywords

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