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Title: Reactive Adsorption of Humid SO2 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 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 desulfurizationmore » 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)
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. https://doi.org/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. https://doi.org/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. https://doi.org/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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Works referenced in this record:

Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks
journal, September 2016


Air Emissions of Sulphur Dioxide From Gasoline and Diesel Consumption in the Southwestern States of Nigeria
journal, March 2015


Synthesis, characterization and experimental investigation of Cu-BTC as CO2 adsorbent from flue gas
journal, April 2012


Fabrication of Metal–Organic Framework and Infinite Coordination Polymer Nanosheets by the Spray Technique
journal, January 2017


Two-Dimensional Metal-Organic Framework Nanosheets
journal, December 2016


Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets
journal, September 2017


Transition Metal-Catalyzed Oxidation of Sulfur(IV) Oxides. Atmospheric-Relevant Processes and Mechanisms
journal, January 1995

  • Brandt, Christian; van Eldik, Rudi
  • Chemical Reviews, Vol. 95, Issue 1
  • DOI: 10.1021/cr00033a006

Immobilization of Cu(II) in KIT-6 supported Co3O4 and catalytic performance for epoxidation of styrene
journal, December 2015


Infrared and Raman spectra of phtalate, isophtalate and terephtalate ions
journal, January 1979


Vibrational and Electronic Spectroscopy of Sulfuric Acid Vapor
journal, January 2003

  • Hintze, Paul E.; Kjaergaard, Henrik G.; Vaida, Veronica
  • The Journal of Physical Chemistry A, Vol. 107, Issue 8
  • DOI: 10.1021/jp0263626

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