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Title: Site-Selective Catalysis of a Multifunctional Linear Molecule: The Steric Hindrance of Metal–Organic Framework Channels

Abstract

The site-selective reaction of a multifunctional linear molecule requires a suitable catalyst possessing both uniform narrow channel to limit the molecule rotation and a designed active site in the channel. Recently, nanoparticles (NPs) were incorporated in metal–organic frameworks (MOFs) with the tailorable porosity and ordered nanochannel, which makes these materials (NPs/MOFs) highly promising candidates as catalytic nanoreactors in the field of heterogeneous catalysis. Inspired by a “Gondola” sailing in narrow “Venetian Canal” without sufficient space for a U-turn, a simple heterogeneous catalyst based on NPs/MOFs is developed here that exhibits site-selectivity for the oxidation of diols by restricting the random rotation of the molecule (the “Gondola”) in the limited space of the MOF channel (the narrow “Venetian Canal”), thereby protecting the middle functional group via steric hindrance. This strategy is not limited to the oxidation of diols, but can be extended to the site-selective reaction of many similar multifunctional linear molecules, such as the reduction of alkadienes.

Authors:
 [1];  [1];  [2];  [1];  [1];  [2];  [3];  [4];  [5];  [1];  [1]
  1. Nanjing Tech Univ. (China). Key Lab. of Flexible Electronics (KLOFE). Inst. of Advanced Materials (IAM)
  2. Nanyang Technological Univ. (Singapore). School of Materials Science and Engineering
  3. Nanyang Technological Univ. (Singapore). Division of Chemistry and Biological Chemistry. School of Physical and Mathematical Sciences
  4. Nanjing Tech Univ. (China). Inst. of Advanced Synthesis (IAS)
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Nanjing Tech Univ. (China)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC); National Key R&D Program of China; National Science Foundation for Distinguished Young Scholars (China); National Natural Science Foundation of China (NNSFC); Jiangsu Provincial Funds for Natural Science Foundation (China); Program for Outstanding Young Scholars from the Organization Department of the CPC Central Committee (China); National Key Basic Research Program of China
OSTI Identifier:
1484038
Grant/Contract Number:  
AC02-06CH11357; 2017YFA0207201; 21625401; 21604038; 21574065; 21504043; 21604040; BK20160975; BK20160981; BK20160993; 2015CB932200
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 23; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; metal nanoparticles; metal–organic frameworks; porous structure; site-selective catalysis; steric hindrance

Citation Formats

Zhang, Weina, Zheng, Bing, Shi, Wenxiong, Chen, Xinyi, Xu, Zhiling, Li, Shuzhou, Chi, Yonggui Robin, Yang, Yanhui, Lu, Jun, Huang, Wei, and Huo, Fengwei. Site-Selective Catalysis of a Multifunctional Linear Molecule: The Steric Hindrance of Metal–Organic Framework Channels. United States: N. p., 2018. Web. doi:10.1002/adma.201800643.
Zhang, Weina, Zheng, Bing, Shi, Wenxiong, Chen, Xinyi, Xu, Zhiling, Li, Shuzhou, Chi, Yonggui Robin, Yang, Yanhui, Lu, Jun, Huang, Wei, & Huo, Fengwei. Site-Selective Catalysis of a Multifunctional Linear Molecule: The Steric Hindrance of Metal–Organic Framework Channels. United States. doi:10.1002/adma.201800643.
Zhang, Weina, Zheng, Bing, Shi, Wenxiong, Chen, Xinyi, Xu, Zhiling, Li, Shuzhou, Chi, Yonggui Robin, Yang, Yanhui, Lu, Jun, Huang, Wei, and Huo, Fengwei. Mon . "Site-Selective Catalysis of a Multifunctional Linear Molecule: The Steric Hindrance of Metal–Organic Framework Channels". United States. doi:10.1002/adma.201800643. https://www.osti.gov/servlets/purl/1484038.
@article{osti_1484038,
title = {Site-Selective Catalysis of a Multifunctional Linear Molecule: The Steric Hindrance of Metal–Organic Framework Channels},
author = {Zhang, Weina and Zheng, Bing and Shi, Wenxiong and Chen, Xinyi and Xu, Zhiling and Li, Shuzhou and Chi, Yonggui Robin and Yang, Yanhui and Lu, Jun and Huang, Wei and Huo, Fengwei},
abstractNote = {The site-selective reaction of a multifunctional linear molecule requires a suitable catalyst possessing both uniform narrow channel to limit the molecule rotation and a designed active site in the channel. Recently, nanoparticles (NPs) were incorporated in metal–organic frameworks (MOFs) with the tailorable porosity and ordered nanochannel, which makes these materials (NPs/MOFs) highly promising candidates as catalytic nanoreactors in the field of heterogeneous catalysis. Inspired by a “Gondola” sailing in narrow “Venetian Canal” without sufficient space for a U-turn, a simple heterogeneous catalyst based on NPs/MOFs is developed here that exhibits site-selectivity for the oxidation of diols by restricting the random rotation of the molecule (the “Gondola”) in the limited space of the MOF channel (the narrow “Venetian Canal”), thereby protecting the middle functional group via steric hindrance. This strategy is not limited to the oxidation of diols, but can be extended to the site-selective reaction of many similar multifunctional linear molecules, such as the reduction of alkadienes.},
doi = {10.1002/adma.201800643},
journal = {Advanced Materials},
number = 23,
volume = 30,
place = {United States},
year = {2018},
month = {4}
}

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Cited by: 12 works
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Figures / Tables:

Scheme 1 Scheme 1: Schematic representation of the site-selective catalysis of multifunctional linear molecule. The multifunctional linear molecule corresponds to the “Gondola” and each channel of the MOF corresponds to a narrow “Venetian Canal.” When the “Gondola” sails into a narrow “Venetian Canal,” it can only proceed directly ahead because the narrowmore » canal does not supply sufficient space for rotation of the “Gondola.” Hence, even though the side of the middle group enters the MOF pore apertures, reaction rarely occurs because of the lack of space for the middle group rotation.« less

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    Works referencing / citing this record:

    Metal-Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives
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    Metal-Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.