Accelerated Computational Analysis of Metal–Organic Frameworks for Oxidation Catalysis

Vogiatzis, Konstantinos D.; Haldoupis, Emmanuel; Xiao, Dianne J.; Long, Jeffrey R.; Siepmann, J. Ilja; Gagliardi, Laura

doi:10.1021/acs.jpcc.6b07115

Title: Accelerated Computational Analysis of Metal–Organic Frameworks for Oxidation Catalysis

Journal Article · Thu Jul 28 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b07115· OSTI ID:1326100

Vogiatzis, Konstantinos D. ^[1]; Haldoupis, Emmanuel ^[1]; Xiao, Dianne J. ^[2]; Long, Jeffrey R. ^[3]; Siepmann, J. Ilja ^[1]; Gagliardi, Laura ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

High-spin iron(IV)–oxo compounds are known to activate strong C–H bonds. Stabilizing the high-spin S = 2 electronic configuration is difficult in molecular species for homogeneous catalysis, but recent experimental and computational results suggest this can be achieved in the metal–organic framework Fe₂(dobdc) (dobdc^4– = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogues. With a novel computational screening approach, we have identified three additional frameworks that are predicted to form high-spin iron(IV)–oxo species upon dissociative adsorption of nitrous oxide. The computational work is supported by follow-up experiments which show that, among these three materials, Fe-BTT (BTT^3– = 1,3,5-benzenetristetrazolate) selectively oxidizes ethane to ethanol at 120 °C. Subsequent spectroscopic and cycling studies suggest that framework defects, rather than the bulk framework or extraframework sites, are likely responsible for the observed reactivity. Furthermore, this work shows how computational methods can be used to rapidly identify promising candidate frameworks, and highlights the need for new methods that allow defect sites in metal–organic frameworks to be better understood and exploited for catalysis.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: FG02-12ER16362; SC0008688

OSTI ID:: 1326100

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, Issue 33; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 36 works

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Identifying promising metal–organic frameworks for heterogeneous catalysis via high‐throughput periodic density functional theory Rosen, Andrew S.; Notestein, Justin M.; Snurr, Randall Q. Journal of Computational Chemistry, Vol. 40, Issue 12 https://doi.org/10.1002/jcc.25787	journal	February 2019
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
iron
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Title: Accelerated Computational Analysis of Metal–Organic Frameworks for Oxidation Catalysis

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