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

Hyeju Choi; Aaron W. Peters; Hyunho Noh; Leighanne C. Gallington; Ana E. Platero-Prats; Matthew R. Destefano; Martino Rimoldi; Subhadip Goswami; Karena W. Chapman; Omar K. Farha; Joseph T. Hupp

doi:10.1021/acsaem.9b01664

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

Hyeju Choi, Aaron W. Peters, Hyunho Noh, Leighanne C. Gallington, Ana E. Platero-Prats, Matthew R. Destefano, Martino Rimoldi, Subhadip Goswami, Karena W. Chapman, Omar K. Farha, Joseph T. Hupp

Northwestern University

Research output: Contribution to journal › Article

Abstract

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.

Original language	English
Journal	ACS Applied Energy Materials
DOIs	https://doi.org/10.1021/acsaem.9b01664
Publication status	Accepted/In press - Jan 1 2019

Keywords

ammonia synthesis
metal chalcogenide-based catalyst
metal-organic framework
molecular layer deposition
nitrate photoreduction

ASJC Scopus subject areas

Chemical Engineering (miscellaneous)
Energy Engineering and Power Technology
Electrochemistry
Materials Chemistry
Electrical and Electronic Engineering

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10.1021/acsaem.9b01664

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Choi, H., Peters, A. W., Noh, H., Gallington, L. C., Platero-Prats, A. E., Destefano, M. R., Rimoldi, M., Goswami, S., Chapman, K. W., Farha, O. K., & Hupp, J. T. (Accepted/In press). Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium. ACS Applied Energy Materials. https://doi.org/10.1021/acsaem.9b01664

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.

In: ACS Applied Energy Materials, 01.01.2019.

Research output: Contribution to journal › Article

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. In: ACS Applied Energy Materials. 2019.

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AU - Farha, Omar K.

AU - Hupp, Joseph T.

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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.

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