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Title: Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO 2 Adsorption

Abstract

Porous organic cages (POCs) are emerging porous materials that exhibit intriguing properties in the areas of self-assembly, host-guest interaction, and solution processability. Here in this work, we explore the applicability of POCs as molecular porous supports for polymeric amines. We find that primary amines in poly(ethylenimine) (PEI) can undergo metathesis with the imine bonds present in POCs, resulting in non-porous products. This problem can be overcome by transforming the primary amines in PEI to tertiary amines via methylation. The methylated PEI (mPEI) forms homogeneous composites with amorphous scrambled porous organic cages (ASPOCs) without undesired reactions or phase separation. The microscopic structure of the composites is studied using molecular dynamics simulations. Finally, these composite materials are evaluated as adsorbents for low concentration SO2 (200 ppm) adsorption and show good thermal and cyclic stability.

Authors:
 [1]; ORCiD logo [2];  [1];  [1];  [1]; ORCiD logo [2];  [1];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical & Biomolecular Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computational Sciences and Engineering Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1439925
Alternate Identifier(s):
OSTI ID: 1441050
Grant/Contract Number:  
AC05-00OR22725; SC0012577; ECCS-1542174
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 44; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhu, Guanghui, Carrillo, Jan-Michael Y., Sujan, Achintya, N. Okonkwo, Claudia, Park, Sangjae, Sumpter, Bobby G., Jones, Christopher W., and Lively, Ryan. Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO2 Adsorption. United States: N. p., 2018. Web. doi:10.1039/c8ta02788a.
Zhu, Guanghui, Carrillo, Jan-Michael Y., Sujan, Achintya, N. Okonkwo, Claudia, Park, Sangjae, Sumpter, Bobby G., Jones, Christopher W., & Lively, Ryan. Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO2 Adsorption. United States. doi:10.1039/c8ta02788a.
Zhu, Guanghui, Carrillo, Jan-Michael Y., Sujan, Achintya, N. Okonkwo, Claudia, Park, Sangjae, Sumpter, Bobby G., Jones, Christopher W., and Lively, Ryan. Wed . "Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO2 Adsorption". United States. doi:10.1039/c8ta02788a. https://www.osti.gov/servlets/purl/1439925.
@article{osti_1439925,
title = {Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO2 Adsorption},
author = {Zhu, Guanghui and Carrillo, Jan-Michael Y. and Sujan, Achintya and N. Okonkwo, Claudia and Park, Sangjae and Sumpter, Bobby G. and Jones, Christopher W. and Lively, Ryan},
abstractNote = {Porous organic cages (POCs) are emerging porous materials that exhibit intriguing properties in the areas of self-assembly, host-guest interaction, and solution processability. Here in this work, we explore the applicability of POCs as molecular porous supports for polymeric amines. We find that primary amines in poly(ethylenimine) (PEI) can undergo metathesis with the imine bonds present in POCs, resulting in non-porous products. This problem can be overcome by transforming the primary amines in PEI to tertiary amines via methylation. The methylated PEI (mPEI) forms homogeneous composites with amorphous scrambled porous organic cages (ASPOCs) without undesired reactions or phase separation. The microscopic structure of the composites is studied using molecular dynamics simulations. Finally, these composite materials are evaluated as adsorbents for low concentration SO2 (200 ppm) adsorption and show good thermal and cyclic stability.},
doi = {10.1039/c8ta02788a},
journal = {Journal of Materials Chemistry. A},
number = 44,
volume = 6,
place = {United States},
year = {2018},
month = {5}
}

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