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

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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

Cite this

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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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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Access to Document

10.1021/acsaem.9b01664