Atomic Layer Deposition in a Metal–Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid

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Chemistry of Materials, ISSN: 0897-4756, Vol: 29, Issue: 3, Page: 1058-1068

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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 Gagliardi, Joseph T. Hupp, Omar K. Farha Show More Hide
American Chemical Society (ACS)
Chemistry, Chemical Engineering, Materials Science
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article description
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 ([AlMeOPr], DMAI), a milder precursor than widely used trimethylaluminum (AlMe, 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-AlO. 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-AlO, with promising results in terms of selectivity.

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