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

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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