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

Research output: Contribution to journalArticle

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 languageEnglish
JournalACS Applied Energy Materials
DOIs
Publication statusAccepted/In press - Jan 1 2019

Fingerprint

Photocatalysts
Ammonium Compounds
Nitrates
Iron
Metals
Vapors
Fabrication
Light Metals
Ligands
Catalysts
X ray absorption spectroscopy
Mesoporous materials
Atomic layer deposition
Coordination Complexes
Zirconium
Zirconia
Metal ions
Ions

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

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 journalArticle

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.
@article{e964c02b3b4446768a71799e8912637e,
title = "Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium",
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.",
keywords = "ammonia synthesis, metal chalcogenide-based catalyst, metal-organic framework, molecular layer deposition, nitrate photoreduction",
author = "Hyeju Choi and Peters, {Aaron W.} and Hyunho Noh and Gallington, {Leighanne C.} and Platero-Prats, {Ana E.} and Destefano, {Matthew R.} and Martino Rimoldi and Subhadip Goswami and Chapman, {Karena W.} and Farha, {Omar K.} and Hupp, {Joseph T.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1021/acsaem.9b01664",
language = "English",
journal = "ACS Applied Energy Materials",
issn = "2574-0962",
publisher = "American Chemical Society",

}

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.

PY - 2019/1/1

Y1 - 2019/1/1

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

UR - http://www.scopus.com/inward/record.url?scp=85076243398&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85076243398&partnerID=8YFLogxK

U2 - 10.1021/acsaem.9b01664

DO - 10.1021/acsaem.9b01664

M3 - Article

AN - SCOPUS:85076243398

JO - ACS Applied Energy Materials

JF - ACS Applied Energy Materials

SN - 2574-0962

ER -