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

Journal Article · · ACS Applied Materials and Interfaces
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

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.

Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1574696
Report Number(s):
SAND-2019-10906J; 679413
Journal Information:
ACS Applied Materials and Interfaces, Vol. 11, Issue 46; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 54 works
Citation information provided by
Web of Science

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