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Extending the Compositional Range of Nanocasting in the Oxozirconium Cluster-Based Metal–Organic Framework NU-1000—A Comparative Structural Analysis

Wenyang ZhaoDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United StatesZhao WangDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United StatesCamille D. MalonzoDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United StatesThomas E. WebberDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United StatesAna E. Platero‐PratsX-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, Illinois 60439, United StatesFrancisco J. SotomayorNicolaas A. VermeulenDepartment of Chemistry and Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United StatesTimothy C. WangDepartment of Chemistry and Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United StatesJoseph T. HuppDepartment of Chemistry and Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United StatesOmar K. FarhaDepartment of Chemistry and Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United StatesR. Lee PennDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United StatesKarena W. ChapmanX-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, Illinois 60439, United StatesMatthias ThommesAndreas SteinDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States

2018en

ABI

Annotatsiya

The process of nanocasting in metal–organic frameworks (MOFs) is a versatile approach to modify these porous materials by introducing supporting scaffolds. The nanocast scaffolds can stabilize metal-oxo clusters in MOFs at high temperatures and modulate their chemical environments. Here we demonstrate a range of nanocasting approaches in the MOF NU-1000, which contains hexanuclear oxozirconium clusters (denoted as Zr6 clusters) that are suitable for modification with other metals. We developed methods for introducing SiO2, TiO2, polymeric, and carbon scaffolds into the NU-1000 structure. The responses of NU-1000 toward different scaffold precursors were studied, including the effects on morphology, precursor distribution, and porosity after nanocasting. Upon removal of organic linkers in the MOF by calcination/pyrolysis at 500 °C or above, the Zr6 clusters remained accessible and maintained their Lewis acidity in SiO2 nanocast samples, whereas additional treatment was necessary for Zr6 clusters to become accessible to pyridine probe molecules in carbon nanocast samples. Aggregation of Zr6 clusters was largely prevented with SiO2 or carbon scaffolds even after thermal treatment at 500 °C or above. In the case of titania nanocasting, NU-1000 crystals underwent a pseudomorphic transformation, in which Zr6 clusters reacted with titania to form small aggregates of a Zr/Ti mixed oxide with a local structure resembling that of ZrTi2O6. The ability to maintain high densities of discrete Lewis acidic Zr6 clusters on SiO2 or carbon supports at high temperatures provides a starting point for designing new thermally stable catalysts.

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DOI: 10.1021/acs.chemmater.7b04893

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