Abstract
Benzoic acid modulators that "cap" the Zr 6 -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 [μ 1 -OH + μ 1 -OH 2 ]) up to 5 per node, enabling the "decapped" materials to exhibit enhanced catalytic activity in the oxidation of methyl phenyl sulfide. Computational modeling reveals that the labile Zr-μ 1 -OH groups on these open sites are likely converted into Zr-μ 1 -OOH species that are active in oxidizing the sulfide as well as its sulfoxide product. In solvents such as CH 3 CN and CH 2 Cl 2 , the sulfoxide product can additionally replace the aquo ligands of the Zr-μ 1 -OH 2 moieties to increase the concentration of the sulfoxide adjacent to the active Zr-μ 1 -OOH species, resulting in overoxidation to the sulfone. However, the use of CH 3 OH, 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.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 327-335 |
| Number of pages | 9 |
| Journal | Catalysis Science and Technology |
| Volume | 9 |
| Issue number | 2 |
| DOIs | |
| State | Published - 2019 |
Funding
This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division through a grant (DE FG02-03-ER15457) to the Institute of Catalysis for Energy Processes (ICEP) at Northwestern University (assistantship for R. L.). R. L. additionally acknowledges Sigma Xi for a Grants-in-Aid of Research (G201603152055000) award and support from Northwestern University as a teaching fellow. S. T. N. and H. C. acknowledge support from DTRA (HDTRA1-14-1-0014). R. Q. S. acknowledges support from DTRA (HDTRA1-18-1-0003). M. L. M. acknowledges support from a Ryan Fellowship from the Northwestern University International Institute for Nanotechnology and the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program (32 CFR 168a). M. L. acknowledges summer and academic-year research grants from Northwestern University (NU) and Sigma Xi for a Grants-in-Aid of Research (G201603152055000). NMR and PXRD experiments were carried out at the Integrated Molecular Structure Education and Research Center (IMSERC); SEM images were obtained at the EPIC facility of the Northwestern University Atomic- and Nanoscale Characterization Experimental center. These facilities have received support from one or more of the following sources: the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. ICP-OES analyses were carried out at the Quantitative Bio-element imaging center (QBIC) at NU. We thank Prof. Mercouri Kanatzidis for the use of the adsorption instrument. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy (DE AC02-05CH11231), and the Quest high-performance computing facility at Northwestern University. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division through a grant (DE FG02-03-ER15457) to the Institute of Catalysis for Energy Processes (ICEP) at Northwestern University (assistantship for R. L.). R. L. additionally acknowledges Sigma Xi for a Grants-in-Aid of Research (G201603152055000) award and support from North-western University as a teaching fellow. S. T. N. and H. C. acknowledge support from DTRA (HDTRA1-14-1-0014). R. Q. S. acknowledges support from DTRA (HDTRA1-18-1-0003). M. L. M. acknowledges support from a Ryan Fellowship from the North-western University International Institute for Nanotechnology and the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program (32 CFR 168a). M. L. acknowledges summer and academic-year research grants from North-western University (NU) and Sigma Xi for a Grants-in-Aid of Research (G201603152055000). NMR and PXRD experiments were carried out at the Integrated Molecular Structure Education and Research Center (IMSERC); SEM images were obtained at the EPIC facility of the Northwestern University Atomic-and Nano-scale Characterization Experimental center. These facilities have received support from one or more of the following sources: the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. ICP-OES analyses were carried out at the Quantitative Bio-element imaging center (QBIC) at NU. We thank Prof. Mercouri Kanatzidis for the use of the adsorption instrument. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy (DE AC02-05CH11231), and the Quest high-performance computing facility at Northwestern University.
ASJC Scopus subject areas
- Catalysis