Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOF-based catalytic single sites, preventing their aggregation even after exposure to air at 600 °C. We describe the nanocasting of NU-1000, a MOF with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 °C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.

Recent work has exploited the ability of metal–organic frameworks (MOFs) to isolate Fe sites that mimic the structures of sites in enzymes that catalyze selective oxidations at low temperatures, opening new pathways for the valorization of underutilized feedstocks such as methane. Questions remain as to whether the radical-rebound mechanism commonly invoked in enzymatic and homogeneous systems also applies in these rigid-framework materials, in which resisting the overoxidation of desired products is a major challenge. We demonstrate that MOFs bearing Fe­(II) sites within Fe3-μ3-oxo nodes active for conversion of CH4 + N2O mixtures (368–408 K) require steps beyond the radical-rebound mechanism to protect the desired CH3OH product. Infrared spectra and density functional theory show that CH3OH(g) is stabilized as Fe­(III)–OCH3 groups on the MOF via hydrogen atom transfer with Fe­(III)–OH groups, eliminating water. Consequently, upon addition of a protonic zeolite in inter- and intrapellet mixtures with the MOF, we observed increases in CH3OH selectivity with increasing ratio and proximity of zeolitic H+ to MOF-based Fe­(II) sites, as methanol is protected within the zeolite. We infer from the data that CH3OH(g) is formed via the radical-rebound mechanism on Fe­(II) sites but that subsequent transport and dehydration steps are required to protect CH3OH(g) from overoxidation. The results demonstrate that the radical-rebound mechanism commonly invoked in this chemistry is insufficient to explain the reactivity of these systems, that the selectivity-controlling steps involve both chemical and physical rate phenomena, as well as offering a strategy to mitigate overoxidation in these and similar systems.

A mixed-valence oxotrimer metal–organic framework (MOF), Ni-MIL-127, with a fully coordinated nickel atom and two iron atoms in the inorganic node, generates a missing linker defect upon thermal treatment in helium (>473 K) to engender an open coordination site on nickel which catalyzes propylene oligomerization devoid of any cocatalysts or initiators. This catalyst is stable for ∼20 h on stream at 500 kPa and 473 K, unprecedented for this chemistry. The number of missing linkers on synthesized and activated Ni-MIL-127 MOFs is quantified using temperature-programmed oxidation, 1H nuclear magnetic resonance spectroscopy, and X-ray absorption spectroscopy to be ∼0.7 missing linkers per nickel; thus, a majority of Ni species in the MOF framework catalyze propylene oligomerization. In situ NO titrations under reaction conditions enumerate ∼62% of the nickel atoms as catalytically relevant to validate the defect density upon thermal treatment. Propylene oligomerization rates on Ni-MIL-127 measured at steady state have activation energies of 55–67 kJ mol–1 from 448 to 493 K and are first-order in propylene pressures from 5 to 550 kPa. Density functional theory calculations on cluster models of Ni-MIL-127 are employed to validate the plausibility of the missing linker defect and the Cossee–Arlman mechanism for propylene oligomerization through comparisons between apparent activation energies from steady-state kinetics and computation. This study illustrates how MOF precatalysts engender defective Ni species which exhibit reactivity and stability characteristics that are distinct and can be engineered to improve catalytic activity for olefin oligomerization.