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

• Published in: Chemistry of materials Vol. 29; no. 3; pp. 1058 - 1068
• Main Authors: 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, Gagliardi, Laura, Hupp, Joseph T, Farha, Omar K
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 14.02.2017; American Chemical Society (ACS)
• Subjects: alumina; aluminum; atomic layer deposition; ethanol dehydration; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MATERIALS SCIENCE; metal-organic framework
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.6b03880

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 ([AlMe2O i Pr]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.