Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal-Organic Framework

Matthew C. Simons, Jenny G. Vitillo, Melike Babucci, Adam S. Hoffman, Alexey Boubnov, Michelle L. Beauvais, Zhihengyu Chen, Christopher J. Cramer, Karena W. Chapman, Simon R. Bare, Bruce C. Gates, Connie C. Lu, Laura Gagliardi, Aditya Bhan

Research output: Contribution to journalArticlepeer-review

89 Scopus citations

Abstract

Metal organic frameworks (MOFs), with their crystalline, porous structures, can be synthesized to incorporate a wide range of catalytically active metals in tailored surroundings. These materials have potential as catalysts for conversion of light alkanes, feedstocks available in large quantities from shale gas that are changing the economics of manufacturing commodity chemicals. Mononuclear high-spin (S = 2) Fe(II) sites situated in the nodes of the MOF MIL-100(Fe) convert propane via dehydrogenation, hydroxylation, and overoxidation pathways in reactions with the atomic oxidant N2O. Pair distribution function analysis, N2 adsorption isotherms, X-ray diffraction patterns, and infrared and Raman spectra confirm the single-phase crystallinity and stability of MIL-100(Fe) under reaction conditions (523 K in vacuo, 378-408 K C3H8 + N2O). Density functional theory (DFT) calculations illustrate a reaction mechanism for the formation of 2-propanol, propylene, and 1-propanol involving the oxidation of Fe(II) to Fe(III) via a high-spin Fe(IV)a•O intermediate. The speciation of Fe(II) and Fe(III) in the nodes and their dynamic interchange was characterized by in situ X-ray absorption spectroscopy and ex situ Mössbauer spectroscopy. The catalytic relevance of Fe(II) sites and the number of such sites were determined using in situ chemical titrations with NO. N2 and C3H6 production rates were found to be first-order in N2O partial pressure and zero-order in C3H8 partial pressure, consistent with DFT calculations that predict the reaction of Fe(II) with N2O to be rate determining. DFT calculations using a broken symmetry method show that Fe-trimer nodes affecting reaction contain antiferromagnetically coupled iron species, and highlight the importance of stabilizing high-spin (S = 2) Fe(II) species for effecting alkane oxidation at low temperatures (408 K).

Original languageEnglish (US)
Pages (from-to)18142-18151
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number45
DOIs
StatePublished - Nov 13 2019

Bibliographical note

Publisher Copyright:
Copyright © 2019 American Chemical Society.

MRSEC Support

  • Shared

PubMed: MeSH publication types

  • Journal Article

Fingerprint

Dive into the research topics of 'Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal-Organic Framework'. Together they form a unique fingerprint.

Cite this