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Title: Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis

Abstract

The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognised as a barrier hampering their practical applications. Herein, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100°C, 24 h) and air (up to 390°C) is presented. The bifunctional 1-vinylimidazole (VIm) with both a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches via a coordination process at room temperature, followed by a radical polymerization. Here we call this material Coordination-supported Imidazolate Networks (CINs). Interestingly, CINs are composed of rich mesopores from 2 to 15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. Especially, the stable CINs illustrate a high turnover frequency (TOF) of 779 h -1 in the catalytic oxidation of phenol with H 2O as the green solvent.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [3];  [2]; ORCiD logo [4]
  1. Shanghai Jiao Tong Univ. (China). School of Chemistry and Chemical Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Department of Chemistry, University of Tennessee, Knoxville TN 37996 United States
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1399409
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 42; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; coordination polymers; mesoporous materials; phenol oxidation; polymers; porous ionic liquids

Citation Formats

Zhang, Pengfei, Yang, Shize, Chisholm, Matthew F., Jiang, Xueguang, Huang, Caili, and Dai, Sheng. Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis. United States: N. p., 2017. Web. doi:10.1002/chem.201702430.
Zhang, Pengfei, Yang, Shize, Chisholm, Matthew F., Jiang, Xueguang, Huang, Caili, & Dai, Sheng. Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis. United States. doi:10.1002/chem.201702430.
Zhang, Pengfei, Yang, Shize, Chisholm, Matthew F., Jiang, Xueguang, Huang, Caili, and Dai, Sheng. Mon . "Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis". United States. doi:10.1002/chem.201702430.
@article{osti_1399409,
title = {Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis},
author = {Zhang, Pengfei and Yang, Shize and Chisholm, Matthew F. and Jiang, Xueguang and Huang, Caili and Dai, Sheng},
abstractNote = {The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognised as a barrier hampering their practical applications. Herein, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100°C, 24 h) and air (up to 390°C) is presented. The bifunctional 1-vinylimidazole (VIm) with both a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches via a coordination process at room temperature, followed by a radical polymerization. Here we call this material Coordination-supported Imidazolate Networks (CINs). Interestingly, CINs are composed of rich mesopores from 2 to 15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. Especially, the stable CINs illustrate a high turnover frequency (TOF) of 779 h-1 in the catalytic oxidation of phenol with H2O as the green solvent.},
doi = {10.1002/chem.201702430},
journal = {Chemistry - A European Journal},
number = 42,
volume = 23,
place = {United States},
year = {Mon May 29 00:00:00 EDT 2017},
month = {Mon May 29 00:00:00 EDT 2017}
}

Journal Article:
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  • A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with themore » sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network structures. • Halogen and hydrogen bonding interactions lead to various supramolecular networks. • Luminescent and magnetic properties were studied and discussed in detail.« less
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