Reactive Adsorption of Humid SO2 on Metal–Organic Framework Nanosheets

Elder, Alexander C.; Bhattacharyya, Souryadeep; Nair, Sankar; Orlando, Thomas M.

doi:10.1021/acs.jpcc.8b00999

Title: Reactive Adsorption of Humid SO₂ on Metal–Organic Framework Nanosheets

Journal Article · Tue Apr 24 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b00999· OSTI ID:1470626

Elder, Alexander C. ^[1]; Bhattacharyya, Souryadeep ^[1];

^[1]; Orlando, Thomas M. ^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)

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.

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Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012577

OSTI ID:: 1470626

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, 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; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 27 works

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Title: Reactive Adsorption of Humid SO2 on Metal–Organic Framework Nanosheets

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Title: Reactive Adsorption of Humid SO₂ on Metal–Organic Framework Nanosheets