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

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.

doi:10.1021/acsaem.9b01664

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

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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:

Choi, Hyeju ^[1];

^[1];

^[2];

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^[3];

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Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Stony Brook Univ., NY (United States)

Publication Date:: Thu Nov 14 00:00:00 EST 2019

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.  doi:10.1021/acsaem.9b01664.

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                    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

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                    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.

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@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         = {Thu Nov 14 00:00:00 EST 2019},

  month        = {Thu Nov 14 00:00:00 EST 2019}

}

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