Electric field-induced selective catalysis of single-molecule reaction

被引：202

作者：

Huang, Xiaoyan ^{[1
]}

Tang, Chun ^{[1
]}

Li, Jieqiong ^{[1
]}

Chen, Li-Chuan ^{[1
,2
]}

Zheng, Jueting ^{[1
]}

Zhang, Pei ^{[1
]}

Le, Jiabo ^{[1
]}

Li, Ruihao ^{[1
]}

Li, Xiaohui ^{[1
]}

Liu, Junyang ^{[1
]}

Yang, Yang ^{[1
]}

Shi, Jia ^{[1
]}

Chen, Zhaobin ^{[1
]}

Bai, Mindong ^{[3
]}

Zhang, Hao-Li ^{[2
]}

Xia, Haiping ^{[1
]}

Cheng, Jun ^{[1
]}

Tian, Zhong-Qun ^{[1
]}

Hong, Wenjing ^{[1
]}

机构：

[1] Xiamen Univ, Natl Engn Lab Green Chem Prod Alcohols Ethers Est, iChEM Collaborat Innovat Ctr Chem Energy Mat, State Key Lab Phys Chem Solid Surfaces,Coll Chem, Xiamen 361005, Fujian, Peoples R China

[2] Lanzhou Univ, Coll Chem & Chem Engn, State Key Lab Appl Organ Chem, Lanzhou 730000, Gansu, Peoples R China

[3] Xiamen Univ, Coll Environm & Ecol, Xiamen 361005, Fujian, Peoples R China

来源：

SCIENCE ADVANCES | 2019年 / 5卷 / 06期

基金：

中国国家自然科学基金; 中国博士后科学基金; 国家重点研发计划;

关键词：

ELECTROSTATIC CATALYSIS; ORBITAL METHODS; CONDUCTANCE; ACTIVATION; JUNCTION; AROMATICITY; CONJUGATION; LIGATION;

D O I：

10.1126/sciadv.aaw3072

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Oriented external electric fields (OEEFs) offer a unique chance to tune catalytic selectivity by orienting the alignment of the electric field along the axis of the activated bond for a specific chemical reaction; however, they remain a key experimental challenge. Here, we experimentally and theoretically investigated the OEEF-induced selective catalysis in a two-step cascade reaction of the Diels-Alder addition followed by an aromatization process. Characterized by the mechanically controllable break junction (MCBJ) technique in the nanogap and confirmed by nuclear magnetic resonance (NMR) in bottles, OEEFs are found to selectively catalyze the aromatization reaction by one order of magnitude owing to the alignment of the electric field on the reaction axis. Meanwhile, the Diels-Alder reaction remained unchanged since its reaction axis is orthogonal to the electric fields. This orientation-selective catalytic effect of OEEFs reveals that chemical reactions can be selectively manipulated through the elegant alignment between the electric fields and the reaction axis.

引用

页数：7

共 59 条

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