TY - JOUR
T1 - Stabilization of Photocatalytically Active Uranyl Species in a Uranyl-Organic Framework for Heterogeneous Alkane Fluorination Driven by Visible Light
AU - Zhang, Xuan
AU - Li, Peng
AU - Krzyaniak, Matthew
AU - Krzyaniak, Matthew
AU - Knapp, Julia
AU - Knapp, Julia
AU - Wasielewski, Michael R.
AU - Farha, Omar K.
N1 - Funding Information:
O.K.F. acknowledges support from the U.S. Department of Energy, National Nuclear Security Administration, under Award DE-NA0003763 and gratefully acknowledges Northwestern University for financial support. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-FG02-99ER14999 (M.R.W.). The authors acknowledge the Integrated Molecular Structure Education and Research Center at Northwestern University, which has received support from the National Science Foundation (NSF; Grants CHE-1048773 and DMR-0521267). This work made use of the Keck-II Facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205), the MRSEC program at the Materials Research Center (NSF Grant DMR-1720139), the IIN, the Keck Foundation, and the State of Illinois, through the IIN.
PY - 2020
Y1 - 2020
N2 - When photoactivated, the uranyl ion is a powerful oxidant capable of abstracting hydrogen atoms from nonactivated C-H bonds. However, the highly reactive singly reduced [UVO2]+ intermediate is unstable with respect to disproportionation to the uranyl dication and insoluble tetravalent uranium phases, which limits the usage of uranyl ions as robust photocatalysts. Herein, we demonstrate that photoactivated uranyl ions can be stabilized by immobilizing and separating them spatially in a uranyl-organic framework heterogeneous catalyst, NU-1301. The visible-light-photoactivated uranyl ions in NU-1301 exhibited longer-lived U(V) and radicals than those in homogeneous counterparts, as evidenced by X-ray photoelectron spectroscopy and time-dependent electron paramagnetic resonance, leading to higher turnovers and enhanced stability for the fluorination of nonactivated alkanes.
AB - When photoactivated, the uranyl ion is a powerful oxidant capable of abstracting hydrogen atoms from nonactivated C-H bonds. However, the highly reactive singly reduced [UVO2]+ intermediate is unstable with respect to disproportionation to the uranyl dication and insoluble tetravalent uranium phases, which limits the usage of uranyl ions as robust photocatalysts. Herein, we demonstrate that photoactivated uranyl ions can be stabilized by immobilizing and separating them spatially in a uranyl-organic framework heterogeneous catalyst, NU-1301. The visible-light-photoactivated uranyl ions in NU-1301 exhibited longer-lived U(V) and radicals than those in homogeneous counterparts, as evidenced by X-ray photoelectron spectroscopy and time-dependent electron paramagnetic resonance, leading to higher turnovers and enhanced stability for the fluorination of nonactivated alkanes.
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U2 - 10.1021/acs.inorgchem.0c00850
DO - 10.1021/acs.inorgchem.0c00850
M3 - Article
C2 - 32484338
AN - SCOPUS:85086841173
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
ER -