Optimizing Open Iron Sites in Metal–Organic Frameworks for Ethane Oxidation: A First-Principles Study

Liao, Peilin; Getman, Rachel B.; Snurr, Randall Q.

doi:10.1021/acsami.7b02195

Title: Optimizing Open Iron Sites in Metal–Organic Frameworks for Ethane Oxidation: A First-Principles Study

Journal Article · 10 April 2017 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.7b02195 · OSTI ID:1371789

Liao, Peilin ^[1]; Getman, Rachel B. ^[2];

^[3]

Northwestern Univ., Evanston, IL (United States); Purdue Univ., West Lafayette, IN (United States)
Clemson Univ., SC (United States)
Northwestern Univ., Evanston, IL (United States)

Activation of the C-H bonds in ethane to form ethanol is a highly desirable, yet challenging, reaction. Metal- organic frameworks (MOFs) with open Fe sites are promising candidates for catalyzing this reaction. One advantage of MOFs is their modular construction from inorganic nodes and organic linkers, allowing for flexible design and detailed control of properties. In this work, we studied a series of single-metal atom Fe model systems with ligands that are commonly used as MOF linkers and tried to understand how one can design an optimal Fe catalyst. We found linear relationships between the binding enthalpy of oxygen to the Fe sites and common descriptors for catalytic reactions, such as the Fe 3d energy levels in different reaction intermediates. We further analyzed the three highest-barrier steps in the ethane oxidation cycle (including desorption of the product) with the Fe 3d energy levels. Volcano relationships are revealed with peaks toward higher Fe 3d energy and stronger electron-donating group functionalization of linkers. Furthermore, we found that the Fe 3d energy levels positively correlate with the electron-donating strength of functional groups on the linkers. Finally, we validated our hypotheses on larger models of MOF-74 iron sites. Compared with MOF-74, functionalizing the MOF-74 linkers with NH₂ groups lowers the enthalpic barrier for the most endothermic step in the reaction cycle. Our findings provide insight for catalyst optimization and point out directions for future experimental efforts.

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Research Organization:: Northwestern Univ., Evanston, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012702; AC02-05CH11231

OSTI ID:: 1371789

Alternate ID(s):: OSTI ID: 1507736

Journal Information:: ACS Applied Materials and Interfaces, Vol. 9, Issue 39; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 42 works

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
catalyst screening
DFT
ethane
ethanol
metal−organic frameworks
nitrous oxide