Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting

Camille D. Malonzo, Sammy M. Shaker, Limin Ren, Steven D. Prinslow, Ana E. Platero-Prats, Leighanne C. Gallington, Joshua Borycz, Anthony B. Thompson, Timothy C. Wang, Omar K. Farha, Joseph T Hupp, Connie C. Lu, Karena W. Chapman, Jason C. Myers, R. Lee Penn, Laura Gagliardi, Michael Tsapatsis, Andreas Stein

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOF-based catalytic single sites, preventing their aggregation even after exposure to air at 600°C. We describe the nanocasting of NU-1000, a MOF with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600°C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.

Original languageEnglish
Pages (from-to)2739-2748
Number of pages10
JournalJournal of the American Chemical Society
Volume138
Issue number8
DOIs
Publication statusPublished - Mar 2 2016

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Catalytic Domain
Stabilization
Hot Temperature
Metals
Silicon Dioxide
Catalyst activity
Temperature
Silica
Agglomeration
Air
Synchrotrons
Isomerization
X ray scattering
Acidity
Scaffolds
Pyridine
Adsorption
Distribution functions
Density functional theory
Glucose

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Malonzo, C. D., Shaker, S. M., Ren, L., Prinslow, S. D., Platero-Prats, A. E., Gallington, L. C., ... Stein, A. (2016). Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting. Journal of the American Chemical Society, 138(8), 2739-2748. https://doi.org/10.1021/jacs.5b12688

Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting. / Malonzo, Camille D.; Shaker, Sammy M.; Ren, Limin; Prinslow, Steven D.; Platero-Prats, Ana E.; Gallington, Leighanne C.; Borycz, Joshua; Thompson, Anthony B.; Wang, Timothy C.; Farha, Omar K.; Hupp, Joseph T; Lu, Connie C.; Chapman, Karena W.; Myers, Jason C.; Penn, R. Lee; Gagliardi, Laura; Tsapatsis, Michael; Stein, Andreas.

In: Journal of the American Chemical Society, Vol. 138, No. 8, 02.03.2016, p. 2739-2748.

Research output: Contribution to journalArticle

Malonzo, CD, Shaker, SM, Ren, L, Prinslow, SD, Platero-Prats, AE, Gallington, LC, Borycz, J, Thompson, AB, Wang, TC, Farha, OK, Hupp, JT, Lu, CC, Chapman, KW, Myers, JC, Penn, RL, Gagliardi, L, Tsapatsis, M & Stein, A 2016, 'Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting', Journal of the American Chemical Society, vol. 138, no. 8, pp. 2739-2748. https://doi.org/10.1021/jacs.5b12688
Malonzo, Camille D. ; Shaker, Sammy M. ; Ren, Limin ; Prinslow, Steven D. ; Platero-Prats, Ana E. ; Gallington, Leighanne C. ; Borycz, Joshua ; Thompson, Anthony B. ; Wang, Timothy C. ; Farha, Omar K. ; Hupp, Joseph T ; Lu, Connie C. ; Chapman, Karena W. ; Myers, Jason C. ; Penn, R. Lee ; Gagliardi, Laura ; Tsapatsis, Michael ; Stein, Andreas. / Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 8. pp. 2739-2748.
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