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Title: Stability of Zeolitic Imidazolate Frameworks in NO 2

Abstract

The use of nanoporous zeolitic imidazolate frameworks (ZIFs) in separation processes is promising, but the presence of acid gases such as SO x or NO x in process streams can have detrimental results. Although we have recently developed a mechanistic picture of SO x–ZIF interactions, here we describe the remarkably different effects of NO 2 on ZIFs. ZIFs with a representative range of SO x stabilities are all unstable—as defined by loss of crystallinity and porosity—in dry and humid NO 2, whereas most ZIFs are stable in dry SO x and some even in humid SO x. A detailed mechanism is developed based on Fourier transform infrared spectroscopy and density functional theory calculations. H-abstraction by free radical NO 2 and subsequent acidic species formation are the major degradation pathways, while adsorbed HNO 3 formation in humid conditions is an additional pathway in hydrophilic ZIFs. These findings strongly suggest that new strategies to stabilize ZIFs/metal–organic frameworks toward NO 2 attack are required.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC); Georgia Inst. of Technology, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566526
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 4; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); defects; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Bhattacharyya, Souryadeep, Han, Rebecca, Joshi, Jayraj N., Zhu, Guanghui, Lively, Ryan P., Walton, Krista S., Sholl, David S., and Nair, Sankar. Stability of Zeolitic Imidazolate Frameworks in NO2. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.8b11377.
Bhattacharyya, Souryadeep, Han, Rebecca, Joshi, Jayraj N., Zhu, Guanghui, Lively, Ryan P., Walton, Krista S., Sholl, David S., & Nair, Sankar. Stability of Zeolitic Imidazolate Frameworks in NO2. United States. doi:10.1021/acs.jpcc.8b11377.
Bhattacharyya, Souryadeep, Han, Rebecca, Joshi, Jayraj N., Zhu, Guanghui, Lively, Ryan P., Walton, Krista S., Sholl, David S., and Nair, Sankar. Fri . "Stability of Zeolitic Imidazolate Frameworks in NO2". United States. doi:10.1021/acs.jpcc.8b11377.
@article{osti_1566526,
title = {Stability of Zeolitic Imidazolate Frameworks in NO2},
author = {Bhattacharyya, Souryadeep and Han, Rebecca and Joshi, Jayraj N. and Zhu, Guanghui and Lively, Ryan P. and Walton, Krista S. and Sholl, David S. and Nair, Sankar},
abstractNote = {The use of nanoporous zeolitic imidazolate frameworks (ZIFs) in separation processes is promising, but the presence of acid gases such as SOx or NOx in process streams can have detrimental results. Although we have recently developed a mechanistic picture of SOx–ZIF interactions, here we describe the remarkably different effects of NO2 on ZIFs. ZIFs with a representative range of SOx stabilities are all unstable—as defined by loss of crystallinity and porosity—in dry and humid NO2, whereas most ZIFs are stable in dry SOx and some even in humid SOx. A detailed mechanism is developed based on Fourier transform infrared spectroscopy and density functional theory calculations. H-abstraction by free radical NO2 and subsequent acidic species formation are the major degradation pathways, while adsorbed HNO3 formation in humid conditions is an additional pathway in hydrophilic ZIFs. These findings strongly suggest that new strategies to stabilize ZIFs/metal–organic frameworks toward NO2 attack are required.},
doi = {10.1021/acs.jpcc.8b11377},
journal = {Journal of Physical Chemistry. C},
number = 4,
volume = 123,
place = {United States},
year = {2019},
month = {1}
}

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This content will become publicly available on January 4, 2020
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