The Synthesis Science of Targeted Vapor-Phase Metal-Organic Framework Postmodification.

The postmodification of metal organic frameworks (MOFs) affords exceedingly high surface area materials with precisely installed chemical features, which provide new opportunities for detailed structure-function correlation in the field of catalysis. Here, we significantly expand upon the number of vapor-phase postmodification processes reported to date through screening a library of atomic layer deposition (ALD) precursors, which span metals across the periodic table and which include ligands from four distinct precursor classes. With a large library of precursors and synthesis conditions, we discern trends in the compatibility of precursor classes for well-behaved ALD in MOFs (AIM) and identify challenges and solutions to more precise postsynthetic modification.

Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework.

Mononuclear and dinuclear copper species were synthesized at the nodes of an NU-1000 metal-organic framework (MOF) via cation exchange and subsequent oxidation at 200 °C in oxygen. Copper-exchanged MOFs are active for selectively converting methane to methanol at 150-200 °C. At 150 °C and 1 bar methane, approximately a third of the copper centers are involved in converting methane to methanol.

Quantum confinement in few layer SnS nanosheets.

Orthorhombic tin monosulfide (SnS) consists of layers of covalently bound Sn and S atoms held together by weak van der Waals forces and is a stable two-dimensional material with potentially useful properties in emerging applications such as valleytronics. Large-scale sustainable synthesis of few-layer (e.g.

Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes.

Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter ion (Ga) is preassembled and delivered onto a metal-organic framework (MOF) support, NU-1000.

Application and Limitations of Nanocasting in Metal-Organic Frameworks.

Nanocasting can be a useful strategy to transfer the catalytic metal clusters in metal-organic frameworks (MOFs) to an all-inorganic support such as silica. The incorporation of silica in the MOF pores as a secondary support has the potential to extend the application of the highly tunable metal-based active sites in MOFs to high temperature catalysis. Here, we demonstrate the applicability of the nanocasting method to a range of MOFs that incorporate catalytically attractive hexazirconium, hexacerium, or pentanickel oxide-based clusters (UiO-66, (Ce)UiO-66, (Ce)UiO-67, (Ce)MOF-808, DUT-9, and In- and Ni-postmetalated NU-1000).

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions.

Role of a Modulator in the Synthesis of Phase-Pure NU-1000.

NU-1000 is a robust, mesoporous metal-organic framework (MOF) with hexazirconium nodes ([ZrOH], referred to as oxo-Zr nodes) that can be synthesized by combining a solution of ZrOCl·8HO and a benzoic acid modulator in N,N-dimethylformamide with a solution of linker (1,3,6,8-tetrakis(p-benzoic acid)pyrene, referred to as HTBAPy) and by aging at an elevated temperature. Typically, the resulting crystals are primarily composed of NU-1000 domains that crystallize with a more dense phase that shares structural similarity with NU-901, which is an MOF composed of the same linker molecules and nodes. Density differences between the two polymorphs arise from the differences in the node orientation: in NU-1000, the oxo-Zr nodes rotate 120° from node to node, whereas in NU-901, all nodes are aligned in parallel.