TY - JOUR
T1 - Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium
AU - Choi, Hyeju
AU - Peters, Aaron W.
AU - Noh, Hyunho
AU - Gallington, Leighanne C.
AU - Platero-Prats, Ana E.
AU - Destefano, Matthew R.
AU - Rimoldi, Martino
AU - Goswami, Subhadip
AU - Chapman, Karena W.
AU - Farha, Omar K.
AU - Hupp, Joseph T.
N1 - Funding Information:
This work was supported as part of the Center for Light Energy Activated Redox Processes, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0001059). H.N. gratefully acknowledges support from the Ryan Fellowship program of the Northwestern University International Institute of Nanotechnology. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). This work made use of the EPIC facility of Northwestern University’s NU ANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the IIN; the Keck Foundation; and the State of Illinois, through the IIN. This work made use of the J.B.Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University and the SHyNE Resource (NSF ECCS-1542205.). Work done at Argonne was performed using the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. We thank Prof. J. M. Notestein for the use of his DR-UV spectrometer.
PY - 2019/12/23
Y1 - 2019/12/23
N2 - We describe a method for synthesizing a nitrate reduction catalyst within a metal-organic framework (MOF). The MOF NU-1000, a zirconium-based mesoporous material, is exposed by using atomic layer deposition (ALD) to a vaporous iron amidinate coordination complex and subsequently a dodecanethiol ligand to synthesize an iron thiolate cluster grafted on the zirconium oxide nodes. Structural identification of the cluster is conducted through X-ray absorption spectroscopy (XAS) and differential envelope density (DED) analyses. Once submerged in an aqueous solution containing nitrate (30 ppm of N) and irradiated with light, the MOF/iron thiolate cluster assembly can photochemically transform the nitrate to ammonium ions. We suggest that sequential, self-limiting, atomic (metal ion), and molecular (ligand) deposition onto the reactive nodes of chemically and thermally stable MOFs could prove to be a versatile and attractive method for obtaining nature-inspired chemical catalysts.
AB - We describe a method for synthesizing a nitrate reduction catalyst within a metal-organic framework (MOF). The MOF NU-1000, a zirconium-based mesoporous material, is exposed by using atomic layer deposition (ALD) to a vaporous iron amidinate coordination complex and subsequently a dodecanethiol ligand to synthesize an iron thiolate cluster grafted on the zirconium oxide nodes. Structural identification of the cluster is conducted through X-ray absorption spectroscopy (XAS) and differential envelope density (DED) analyses. Once submerged in an aqueous solution containing nitrate (30 ppm of N) and irradiated with light, the MOF/iron thiolate cluster assembly can photochemically transform the nitrate to ammonium ions. We suggest that sequential, self-limiting, atomic (metal ion), and molecular (ligand) deposition onto the reactive nodes of chemically and thermally stable MOFs could prove to be a versatile and attractive method for obtaining nature-inspired chemical catalysts.
KW - ammonia synthesis
KW - metal chalcogenide-based catalyst
KW - metal-organic framework
KW - molecular layer deposition
KW - nitrate photoreduction
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U2 - 10.1021/acsaem.9b01664
DO - 10.1021/acsaem.9b01664
M3 - Article
AN - SCOPUS:85076243398
VL - 2
SP - 8695
EP - 8700
JO - ACS Applied Energy Materials
JF - ACS Applied Energy Materials
SN - 2574-0962
IS - 12
ER -