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Title: Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium

Abstract

Herein 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.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  3. Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Northwestern University International Institute of Nanotechnology (IIN); National Science Foundation (NSF); State of Illinois; Keck Foundation
OSTI Identifier:
1606545
Grant/Contract Number:  
AC02-06CH11357; SC0001059
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 12; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ammonia synthesis; metal chalcogenide-based catalyst; metal-organic framework; molecular layer deposition; nitrate photoreduction

Citation Formats

Choi, Hyeju, Peters, Aaron W., Noh, Hyunho, Gallington, Leighanne C., Platero-Prats, Ana E., DeStefano, Matthew R., Rimoldi, Martino, Goswami, Subhadip, Chapman, Karena W., Farha, Omar K., and Hupp, Joseph T.. Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium. United States: N. p., 2019. Web. https://doi.org/10.1021/acsaem.9b01664.
Choi, Hyeju, Peters, Aaron W., Noh, Hyunho, Gallington, Leighanne C., Platero-Prats, Ana E., DeStefano, Matthew R., Rimoldi, Martino, Goswami, Subhadip, Chapman, Karena W., Farha, Omar K., & Hupp, Joseph T.. Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium. United States. https://doi.org/10.1021/acsaem.9b01664
Choi, Hyeju, Peters, Aaron W., Noh, Hyunho, Gallington, Leighanne C., Platero-Prats, Ana E., DeStefano, Matthew R., Rimoldi, Martino, Goswami, Subhadip, Chapman, Karena W., Farha, Omar K., and Hupp, Joseph T.. Thu . "Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium". United States. https://doi.org/10.1021/acsaem.9b01664. https://www.osti.gov/servlets/purl/1606545.
@article{osti_1606545,
title = {Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium},
author = {Choi, Hyeju and Peters, Aaron W. and Noh, Hyunho and Gallington, Leighanne C. and Platero-Prats, Ana E. and DeStefano, Matthew R. and Rimoldi, Martino and Goswami, Subhadip and Chapman, Karena W. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Herein 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.},
doi = {10.1021/acsaem.9b01664},
journal = {ACS Applied Energy Materials},
number = 12,
volume = 2,
place = {United States},
year = {2019},
month = {11}
}

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