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Title: NOx Adsorption and Optical Detection in Rare Earth Metal–Organic Frameworks

Abstract

Acid gases (e.g., NOx and SOx), commonly found in complex chemical and petrochemical streams, require material development for their selective adsorption and removal. Here, we report the NOx adsorption properties in a family of rare earth (RE) metal–organic frameworks (MOFs) materials. Fundamental understanding of the structure–property relationship of NOx adsorption in the RE-DOBDC materials platform was sought via a combined experimental and molecular modeling study. No structural change was noted following humid NOx exposure. Density functional theory (DFT) simulations indicated that H2O has a stronger affinity to bind with the metal center than NO2, while NO2 preferentially binds with the DOBDC ligands. Further modeling results indicate no change in binding energy across the RE elements investigated. Also, stabilization of the NO2 and H2O molecules following adsorption was noted, predicted to be due to hydrogen bonding between the framework ligands and the molecules and nanoconfinement within the MOF structure. This interaction also caused distinct changes in emission spectra, identified experimentally. As a result, calculations indicated that this is due to the adsorption of NO2 molecules onto the DOBDC ligand altering the electronic transitions and the resulting photoluminescent properties, a feature that has potential applications in future sensing technologies.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Nanoscale Sciences Dept.
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Geochemistry Dept.
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Material, Physical, and Chemical Sciences Center
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1574696
Report Number(s):
SAND-2019-10906J
Journal ID: ISSN 1944-8244; 679413
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 11; Journal Issue: 46; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; metal−organic frameworks; lanthanide; emission; density functional theory; NOx

Citation Formats

Sava Gallis, Dorina F., Vogel, Dayton J., Vincent, Grace A., Rimsza, Jessica M., and Nenoff, Tina M. NOx Adsorption and Optical Detection in Rare Earth Metal–Organic Frameworks. United States: N. p., 2019. Web. https://doi.org/10.1021/acsami.9b16470.
Sava Gallis, Dorina F., Vogel, Dayton J., Vincent, Grace A., Rimsza, Jessica M., & Nenoff, Tina M. NOx Adsorption and Optical Detection in Rare Earth Metal–Organic Frameworks. United States. https://doi.org/10.1021/acsami.9b16470
Sava Gallis, Dorina F., Vogel, Dayton J., Vincent, Grace A., Rimsza, Jessica M., and Nenoff, Tina M. Mon . "NOx Adsorption and Optical Detection in Rare Earth Metal–Organic Frameworks". United States. https://doi.org/10.1021/acsami.9b16470. https://www.osti.gov/servlets/purl/1574696.
@article{osti_1574696,
title = {NOx Adsorption and Optical Detection in Rare Earth Metal–Organic Frameworks},
author = {Sava Gallis, Dorina F. and Vogel, Dayton J. and Vincent, Grace A. and Rimsza, Jessica M. and Nenoff, Tina M.},
abstractNote = {Acid gases (e.g., NOx and SOx), commonly found in complex chemical and petrochemical streams, require material development for their selective adsorption and removal. Here, we report the NOx adsorption properties in a family of rare earth (RE) metal–organic frameworks (MOFs) materials. Fundamental understanding of the structure–property relationship of NOx adsorption in the RE-DOBDC materials platform was sought via a combined experimental and molecular modeling study. No structural change was noted following humid NOx exposure. Density functional theory (DFT) simulations indicated that H2O has a stronger affinity to bind with the metal center than NO2, while NO2 preferentially binds with the DOBDC ligands. Further modeling results indicate no change in binding energy across the RE elements investigated. Also, stabilization of the NO2 and H2O molecules following adsorption was noted, predicted to be due to hydrogen bonding between the framework ligands and the molecules and nanoconfinement within the MOF structure. This interaction also caused distinct changes in emission spectra, identified experimentally. As a result, calculations indicated that this is due to the adsorption of NO2 molecules onto the DOBDC ligand altering the electronic transitions and the resulting photoluminescent properties, a feature that has potential applications in future sensing technologies.},
doi = {10.1021/acsami.9b16470},
journal = {ACS Applied Materials and Interfaces},
number = 46,
volume = 11,
place = {United States},
year = {2019},
month = {10}
}

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Cited by: 8 works
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Figures / Tables:

Figure 1 Figure 1: (a) N2 sorption isotherms for compounds 1-4 measured at 77K; (b) Powder x-ray diffraction data for pristine and NOx exposed compound 1 after 24 hrs.

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