Targeted Single-Site MOF Node Modification

Trivalent Metal Loading via Atomic Layer Deposition

In Soo Kim, Joshua Borycz, Ana E. Platero-Prats, Samat Tussupbayev, Timothy C. Wang, Omar K. Farha, Joseph T Hupp, Laura Gagliardi, Karena W. Chapman, Christopher J. Cramer, Alex B F Martinson

Research output: Contribution to journalArticle

62 Citations (Scopus)

Abstract

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.

Original languageEnglish
Pages (from-to)4772-4778
Number of pages7
JournalChemistry of Materials
Volume27
Issue number13
DOIs
Publication statusPublished - Jul 14 2015

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Atomic layer deposition
Metals
Atoms
Dehydration
Hydroxyl Radical
Distribution functions
X rays
Water

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Kim, I. S., Borycz, J., Platero-Prats, A. E., Tussupbayev, S., Wang, T. C., Farha, O. K., ... Martinson, A. B. F. (2015). Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition. Chemistry of Materials, 27(13), 4772-4778. https://doi.org/10.1021/acs.chemmater.5b01560

Targeted Single-Site MOF Node Modification : Trivalent Metal Loading via Atomic Layer Deposition. / Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.; Tussupbayev, Samat; Wang, Timothy C.; Farha, Omar K.; Hupp, Joseph T; Gagliardi, Laura; Chapman, Karena W.; Cramer, Christopher J.; Martinson, Alex B F.

In: Chemistry of Materials, Vol. 27, No. 13, 14.07.2015, p. 4772-4778.

Research output: Contribution to journalArticle

Kim, IS, Borycz, J, Platero-Prats, AE, Tussupbayev, S, Wang, TC, Farha, OK, Hupp, JT, Gagliardi, L, Chapman, KW, Cramer, CJ & Martinson, ABF 2015, 'Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition', Chemistry of Materials, vol. 27, no. 13, pp. 4772-4778. https://doi.org/10.1021/acs.chemmater.5b01560
Kim IS, Borycz J, Platero-Prats AE, Tussupbayev S, Wang TC, Farha OK et al. Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition. Chemistry of Materials. 2015 Jul 14;27(13):4772-4778. https://doi.org/10.1021/acs.chemmater.5b01560
Kim, In Soo ; Borycz, Joshua ; Platero-Prats, Ana E. ; Tussupbayev, Samat ; Wang, Timothy C. ; Farha, Omar K. ; Hupp, Joseph T ; Gagliardi, Laura ; Chapman, Karena W. ; Cramer, Christopher J. ; Martinson, Alex B F. / Targeted Single-Site MOF Node Modification : Trivalent Metal Loading via Atomic Layer Deposition. In: Chemistry of Materials. 2015 ; Vol. 27, No. 13. pp. 4772-4778.
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