Transfer hydrogenation of cinnamaldehyde to cinnamyl alcohol in hydrophobically modified core-shell MOFs nanoreactor: Identification of the formed metal-N as the structure of an active site

被引：22

作者：

Cui, Haishuai ^{[1
]}

Liu, Sihua ^{[2
]}

Lv, Yang ^{[1
]}

Wu, Shengtao ^{[1
]}

Wang, Liping ^{[1
]}

Hao, Fang ^{[1
,3
]}

Liu, Pingle ^{[1
,3
,4
]}

Xiong, Wei ^{[1
,4
]}

Luo, Hean ^{[1
,3
,4
]}

机构：

[1] Xiangtan Univ, Coll Chem Engn, Xiangtan 411105, Peoples R China

[2] Hunan Univ Technol, Coll Life Sci & Chem, Zhuzhou 412000, Peoples R China

[3] Xiangtan Univ, Engn Res Ctr Chem Proc Simulat & Optimizat, Minist Educ, Xiangtan 411105, Peoples R China

[4] Xiangtan Univ, Natl & Local United Engn Res Ctr Chem Proc Simula, Xiangtan 411105, Peoples R China

来源：

JOURNAL OF CATALYSIS | 2020年 / 381卷

关键词：

Hydrophobically modified core-shell structure; Metal-organic framework; Cinnamaldehyde; Transfer hydrogenation; Homogeneous reaction; PONNDORF-VERLEY REDUCTION; LAYERED-DOUBLE-HYDROXIDES; IMIDAZOLATE FRAMEWORK-67; CHEMOSELECTIVE REDUCTION; SELECTIVE HYDROGENATION; PHASE HYDROGENATION; BETA ZEOLITE; CATALYST; ZIF-67; MECHANISM;

D O I：

10.1016/j.jcat.2019.11.024

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Zeolitic imidazolate frameworks (ZIFs) were successfully prepared and applied in the environmentally friendly transfer hydrogenation of cinnamaldehyde to cinnamyl alcohol. This was proved to be a homogeneous reaction in heterogeneous system. The experimental results show that ZIFs have better catalytic performance than nitrate. To overcome the recycling of the catalysts, the hydrophobically modified core-shell structure ZIF-67@SiO2-CPTEOS was successfully prepared and hydrogenation took place in this core-shell structure as in a nanoreactor. The reaction rate was enhanced and the active site of the formed metal-N was confined in the core-shell structure nanoreactor. ZIF-67@SiO2-CPTEOS presents better catalytic performance and stability. Furthermore, DFT calculation results show that the activation energy barrier of CoAN in ZIF-67 is lower than that of metallic Co dissociated from Co (NO3)(2)center dot 6H(2)O, which further confirms that introduction of N and thus the formed Co-N bond in ZIF-67 presents higher catalytic activity than that of metal Co. Finally, a possible reaction mechanism is proposed. (C) 2019 Elsevier Inc. All rights reserved.

引用

页码：468 / 481

页数：14