Tuning the Surface Chemistry of Metal Organic Framework Nodes: Proton Topology of the Metal-Oxide-Like Zr6 Nodes of UiO-66 and NU-1000

Yang, Dong; Bernales, Varinia; Islamoglu, Timur; Farha, Omar K.; Hupp, Joseph T.; Cramer, Christopher J.; Gagliardi, Laura; Gates, Bruce C.

doi:10.1021/jacs.6b08273

Tuning the Surface Chemistry of Metal Organic Framework Nodes: Proton Topology of the Metal-Oxide-Like Zr₆ Nodes of UiO-66 and NU-1000

Journal Article · Fri Oct 28 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b08273· OSTI ID:1388680

Yang, Dong ^[1]; Bernales, Varinia ^[2]; Islamoglu, Timur ^[3]; Farha, Omar K. ^[4]; Hupp, Joseph T. ^[3]; Cramer, Christopher J. ^[2]; Gagliardi, Laura ^[2]; Gates, Bruce C. ^[1]

Univ. of California, Davis, CA (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); King Abdul-Aziz Univ., Jeddah (Saudi Arabia)

Some metal organic frameworks (MOFs) incorporate nodes that are nanoscale metal oxides, and the hydroxycontaining functional groups on them provide opportunities for introducing catalytic sites with precisely defined structures. Investigations have been done to understand the structures of these groups on nodes and node vacancies, because, in prospect, atomic-scale modulation of the composition, areal density, and/or siting of the groups would open up possibilities for exquisite tuning of the siting and performance of subsequently anchored catalytic units (e.g., single metal ions, pairs of metal ions, or well-defined metal-ion-containing clusters). In this work we have combined infrared (IR) spectroscopy and density functional theory (DFT) to demonstrate tuning of these sites, namely, hydrogen-bonded OH/OH₂ groups on the Zr₆ nodes of the MOFs UiO-66 and NU-1000 via the intermediacy of node methoxy (or ethoxy) groups formed from methanol (or ethanol). Methoxy (or ethoxy) groups on node vacancy sites are converted to a structure incorporating one vacant Zr site and one terminal OH group per face by reaction with water. Our results highlight how the combination of DFT and IR spectroscopy facilitates the determination of the identity and chemistry of the functional groups on MOF node vacancies and defect sites.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Inorganometallic Catalyst Design (ICDC)

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

Grant/Contract Number:: SC0012702

OSTI ID:: 1388680

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 46 Vol. 138; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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