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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.
Bibliographical noteFunding Information:
This work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0012702. This work made use of the IMSERC facility supported by the National Science Foundation (NSF, DMR-0521267); the J.B. Cohen X-ray Diffraction Facility at the Materials Research Center of NU supported by the MRSEC (NSF, DMR- 1121262); the EPIC facility of the NUANCE Center at NU, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF, NNCI-1542205); the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Metal analysis was performed at the NU Quantitative Bio-element Imaging Center. Gas flow reactions were performed at the NU CleanCat Core facility. A.V., J.L.F., and J.A.L. acknowledge the support by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Work done at Argonne was performed using the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Authors thank Dr. T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland). M.R. was supported by the Swiss National Science Foundation with an "Early Postdoc.Mobility Fellowship". A.E.P.-P. acknowledges a Beatriu de Pino´s fellowship (BP-DGR 2014) from the Ministry of Economy and Knowledge (Catalan Government).
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