Atomic Layer Deposition in a Metal-Organic Framework

Synthesis, Characterization, and Performance of a Solid Acid

Martino Rimoldi, Varinia Bernales, Joshua Borycz, Aleksei Vjunov, Leighanne C. Gallington, Ana E. Platero-Prats, I. S. Kim, John L. Fulton, A. B F Martinson, Johannes A. Lercher, Karena W. Chapman, Christopher J. Cramer, Laura Gagli, Joseph T Hupp, Omar K. Farha

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.

Original languageEnglish
Pages (from-to)1058-1068
Number of pages11
JournalChemistry of Materials
Volume29
Issue number3
DOIs
Publication statusPublished - Feb 14 2017

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Atomic layer deposition
Aluminum
Metals
Acids
Aluminum Oxide
Density functional theory
Zirconium
Oxides

ASJC Scopus subject areas

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

Cite this

Rimoldi, M., Bernales, V., Borycz, J., Vjunov, A., Gallington, L. C., Platero-Prats, A. E., ... Farha, O. K. (2017). Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid. Chemistry of Materials, 29(3), 1058-1068. https://doi.org/10.1021/acs.chemmater.6b03880

Atomic Layer Deposition in a Metal-Organic Framework : Synthesis, Characterization, and Performance of a Solid Acid. / Rimoldi, Martino; Bernales, Varinia; Borycz, Joshua; Vjunov, Aleksei; Gallington, Leighanne C.; Platero-Prats, Ana E.; Kim, I. S.; Fulton, John L.; Martinson, A. B F; Lercher, Johannes A.; Chapman, Karena W.; Cramer, Christopher J.; Gagli, Laura; Hupp, Joseph T; Farha, Omar K.

In: Chemistry of Materials, Vol. 29, No. 3, 14.02.2017, p. 1058-1068.

Research output: Contribution to journalArticle

Rimoldi, M, Bernales, V, Borycz, J, Vjunov, A, Gallington, LC, Platero-Prats, AE, Kim, IS, Fulton, JL, Martinson, ABF, Lercher, JA, Chapman, KW, Cramer, CJ, Gagli, L, Hupp, JT & Farha, OK 2017, 'Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid', Chemistry of Materials, vol. 29, no. 3, pp. 1058-1068. https://doi.org/10.1021/acs.chemmater.6b03880
Rimoldi, Martino ; Bernales, Varinia ; Borycz, Joshua ; Vjunov, Aleksei ; Gallington, Leighanne C. ; Platero-Prats, Ana E. ; Kim, I. S. ; Fulton, John L. ; Martinson, A. B F ; Lercher, Johannes A. ; Chapman, Karena W. ; Cramer, Christopher J. ; Gagli, Laura ; Hupp, Joseph T ; Farha, Omar K. / Atomic Layer Deposition in a Metal-Organic Framework : Synthesis, Characterization, and Performance of a Solid Acid. In: Chemistry of Materials. 2017 ; Vol. 29, No. 3. pp. 1058-1068.
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abstract = "NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.",
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AU - Chapman, Karena W.

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