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Title: Reactive Adsorption of Humid SO 2 on Metal–Organic Framework Nanosheets

Abstract

We explore the interactions of copper, zinc, and cobalt metal–organic framework (MOF) nanosheets with sulfur dioxide (40 ppm in air of 85% relative humidity at 25 °C), with the aim of understanding chemically induced structural changes of open-metal MOFs when exposed to wet acid gases such as flue gas. The structural evolution of the frameworks and the sulfur dioxide adsorption characteristics were studied by vibrational spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The stabilities of the materials under the experimental conditions were established as a function of the metal center, with zinc benzenedicarboxylate (ZnBDC) being the most stable followed by CuBDC and CoBDC. After 80 ppm-days of exposure to humid SO 2 atmosphere, each MOF was found to contain roughly one sulfur atom per metal site. Adsorbed sulfur was found in the +6 and +2 oxidation states with the distribution across these states varying according to the metal in the material. The implication of this finding is that the aqueous chemistry of adsorbed sulfur dioxide is strongly influenced by the metal center. The ability to direct electron transfer to or from adsorbed sulfur while maintaining comparable particle and crystal structure is a powerful potential tool formore » desulfurization technologies.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
Publication Date:
Research Org.:
Georgia Inst. of Technology, Atlanta, GA (United States). Energy Frontier Research Center (EFRC) 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:
1470626
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 19; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MOF; acid gas; sulfur; adsorption; separation

Citation Formats

Elder, Alexander C., Bhattacharyya, Souryadeep, Nair, Sankar, and Orlando, Thomas M. Reactive Adsorption of Humid SO2 on Metal–Organic Framework Nanosheets. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b00999.
Elder, Alexander C., Bhattacharyya, Souryadeep, Nair, Sankar, & Orlando, Thomas M. Reactive Adsorption of Humid SO2 on Metal–Organic Framework Nanosheets. United States. doi:10.1021/acs.jpcc.8b00999.
Elder, Alexander C., Bhattacharyya, Souryadeep, Nair, Sankar, and Orlando, Thomas M. Tue . "Reactive Adsorption of Humid SO2 on Metal–Organic Framework Nanosheets". United States. doi:10.1021/acs.jpcc.8b00999. https://www.osti.gov/servlets/purl/1470626.
@article{osti_1470626,
title = {Reactive Adsorption of Humid SO2 on Metal–Organic Framework Nanosheets},
author = {Elder, Alexander C. and Bhattacharyya, Souryadeep and Nair, Sankar and Orlando, Thomas M.},
abstractNote = {We explore the interactions of copper, zinc, and cobalt metal–organic framework (MOF) nanosheets with sulfur dioxide (40 ppm in air of 85% relative humidity at 25 °C), with the aim of understanding chemically induced structural changes of open-metal MOFs when exposed to wet acid gases such as flue gas. The structural evolution of the frameworks and the sulfur dioxide adsorption characteristics were studied by vibrational spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The stabilities of the materials under the experimental conditions were established as a function of the metal center, with zinc benzenedicarboxylate (ZnBDC) being the most stable followed by CuBDC and CoBDC. After 80 ppm-days of exposure to humid SO2 atmosphere, each MOF was found to contain roughly one sulfur atom per metal site. Adsorbed sulfur was found in the +6 and +2 oxidation states with the distribution across these states varying according to the metal in the material. The implication of this finding is that the aqueous chemistry of adsorbed sulfur dioxide is strongly influenced by the metal center. The ability to direct electron transfer to or from adsorbed sulfur while maintaining comparable particle and crystal structure is a powerful potential tool for desulfurization technologies.},
doi = {10.1021/acs.jpcc.8b00999},
journal = {Journal of Physical Chemistry. C},
number = 19,
volume = 122,
place = {United States},
year = {2018},
month = {4}
}

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