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

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Chemistry of Materials, ISSN: 1520-5002, 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.