Elucidating the mechanism of the UiO-66-catalyzed sulfide oxidation: activity and selectivity enhancements through changes in the node coordination environment and solvent
Abstract
Benzoic acid modulators that “cap” the Zr6-oxo-hydroxo cluster nodes in UiO-66 metal–organic frameworks can be removed to increase the number of “open” sites (i.e., those that are terminated with [μ1-OH + μ1-OH2]) up to 5 per node, enabling the “decapped” materials to exhibit enhanced catalytic activity in the oxidation of methyl phenyl sulfide. Here, computational modeling reveals that the labile Zr-μ1-OH groups on these open sites are likely converted into Zr-μ1-OOH species that are active in oxidizing the sulfide as well as its sulfoxide product. In solvents such as CH3CN and CH2Cl2, the sulfoxide product can additionally replace the aquo ligands of the Zr-μ1-OH2 moieties to increase the concentration of the sulfoxide adjacent to the active Zr-μ1-OOH species, resulting in overoxidation to the sulfone. However, the use of CH3OH, a solvent that can compete with the sulfoxide and suppress this binding mode, can retard the overoxidation and lead to higher selectivities for the sulfoxide product.
- Authors:
-
- Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Sigma Xi; Defense Threat Reduction Agency (DTRA); National Science Foundation (NSF); International Institute for Nanotechnology (IIN); Keck Foundation; State of Illinois
- OSTI Identifier:
- 1543805
- Alternate Identifier(s):
- OSTI ID: 1485709
- Grant/Contract Number:
- AC02-05CH11231; FG02-03ER15457; G201603152055000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Science and Technology
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 2044-4753
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry
Citation Formats
Limvorapitux, Rungmai, Chen, Haoyuan, Mendonca, Matthew L., Liu, Mengtan, Snurr, Randall Q., and Nguyen, SonBinh T. Elucidating the mechanism of the UiO-66-catalyzed sulfide oxidation: activity and selectivity enhancements through changes in the node coordination environment and solvent. United States: N. p., 2018.
Web. doi:10.1039/c8cy01139g.
Limvorapitux, Rungmai, Chen, Haoyuan, Mendonca, Matthew L., Liu, Mengtan, Snurr, Randall Q., & Nguyen, SonBinh T. Elucidating the mechanism of the UiO-66-catalyzed sulfide oxidation: activity and selectivity enhancements through changes in the node coordination environment and solvent. United States. https://doi.org/10.1039/c8cy01139g
Limvorapitux, Rungmai, Chen, Haoyuan, Mendonca, Matthew L., Liu, Mengtan, Snurr, Randall Q., and Nguyen, SonBinh T. Wed .
"Elucidating the mechanism of the UiO-66-catalyzed sulfide oxidation: activity and selectivity enhancements through changes in the node coordination environment and solvent". United States. https://doi.org/10.1039/c8cy01139g. https://www.osti.gov/servlets/purl/1543805.
@article{osti_1543805,
title = {Elucidating the mechanism of the UiO-66-catalyzed sulfide oxidation: activity and selectivity enhancements through changes in the node coordination environment and solvent},
author = {Limvorapitux, Rungmai and Chen, Haoyuan and Mendonca, Matthew L. and Liu, Mengtan and Snurr, Randall Q. and Nguyen, SonBinh T.},
abstractNote = {Benzoic acid modulators that “cap” the Zr6-oxo-hydroxo cluster nodes in UiO-66 metal–organic frameworks can be removed to increase the number of “open” sites (i.e., those that are terminated with [μ1-OH + μ1-OH2]) up to 5 per node, enabling the “decapped” materials to exhibit enhanced catalytic activity in the oxidation of methyl phenyl sulfide. Here, computational modeling reveals that the labile Zr-μ1-OH groups on these open sites are likely converted into Zr-μ1-OOH species that are active in oxidizing the sulfide as well as its sulfoxide product. In solvents such as CH3CN and CH2Cl2, the sulfoxide product can additionally replace the aquo ligands of the Zr-μ1-OH2 moieties to increase the concentration of the sulfoxide adjacent to the active Zr-μ1-OOH species, resulting in overoxidation to the sulfone. However, the use of CH3OH, a solvent that can compete with the sulfoxide and suppress this binding mode, can retard the overoxidation and lead to higher selectivities for the sulfoxide product.},
doi = {10.1039/c8cy01139g},
journal = {Catalysis Science and Technology},
number = 2,
volume = 9,
place = {United States},
year = {Wed Oct 24 00:00:00 EDT 2018},
month = {Wed Oct 24 00:00:00 EDT 2018}
}
Web of Science
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