Quantifying Ligand Binding to the Surface of Metal-Organic Frameworks.

The binding of molecules to the exterior surface of metal-organic frameworks (MOFs) is not a well-understood phenomenon. Herein, the surface chemistry of three MOFs, UiO-66, MIL-88B-NH, and ZIF-8, is investigated using dye-displacement experiments. MOF particle surfaces were modified with ligand-appended BODIPY dyes.

Influence of Polymer Characteristics on the Self-Assembly of Polymer-Grafted Metal-Organic Framework Particles.

Polymer-grafted metal-organic frameworks (MOFs) can combine the properties of MOFs and polymers into a single, matrix-free composite material. Herein, we examine polymer-grafted MOF particles (using UiO-66 as a model system) to examine how the molecular weight, grafting density, and chemical functionality of the polymer graft affects the preparation of free-standing self-assembled MOF monolayers (SAMMs). The physical properties of the monolayers are influenced by the choice of polymer, and robust, flexible monolayers were achieved more readily with poly(methyl acrylate) when compared to poly(methyl methacrylate) or poly(benzyl methacrylate).

Free-standing metal-organic framework (MOF) monolayers by self-assembly of polymer-grafted nanoparticles.

We report a general method for the synthesis of free-standing, self-assembled MOF monolayers (SAMMs) at an air-water interface using polymer-brush coated MOF nanoparticles. UiO-66, UiO-66-NH, and MIL-88B-NH were functionalized with a catechol-bound chain-transfer agent (CTA) to graft poly(methyl methacrylate) (PMMA) from the surface of the MOF using reversible addition-fragmentation chain transfer polymerization (RAFT). The polymer-coated MOFs were self-assembled at the air-water interface into monolayer films ∼250 nm thick and capable of self-supporting at a total area of 40 mm.

Controlled Two-Dimensional Alignment of Metal-Organic Frameworks in Polymer Films.

Controlling the alignment of metal-organic framework (MOF) particles is valueable for fully exploiting the anisotropic properties and porous structure of these materials. Herein, we propose a simple, one-step method that can control the two-dimensional (2D) alignment of MOF particles over large areas. Orientational control is achieved without consideration of the underlying lattice parameters or the need for particle surface modification, but instead was achieved by selection of the casting solvent on a water surface.

MOF-Polymer Hybrid Materials: From Simple Composites to Tailored Architectures.

Metal-organic frameworks (MOFs) are inherently crystalline, brittle porous solids. Conversely, polymers are flexible, malleable, and processable solids that are used for a broad range of commonly used technologies. The stark differences between the nature of MOFs and polymers has motivated efforts to hybridize crystalline MOFs and flexible polymers to produce composites that retain the desired properties of these disparate materials.

Self-Assembly of Metal-Organic Framework (MOF) Nanoparticle Monolayers and Free-Standing Multilayers.

We report the first self-assembled porous monolayer and free-standing multilayer films composed of metal-organic framework (MOF) nanoparticles. Self-assembled MOF monolayers (SAMMs) were assembled at a liquid-air interface to produce films that are 87 wt % (89 vol %) MOF. Monolayer self-assembly was aided by growing a layer of poly(methyl methacrylate) (PMMA) on the particle surface using a histamine anchor.

Halogen bonding in UiO-66 frameworks promotes superior chemical warfare agent simulant degradation.

Herein, a series of halogenated UiO-66 derivatives was synthesized and analyzed for the breakdown of the chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate (DMNP) to analyze ligand effects. UiO-66-I degrades DMNP at a rate four times faster than the most active previously reported MOFs. MOF defects were quantified and ruled out as a cause for increased activity.

Solution-Based Large-Area Assembly of Coaxial Inorganic-Organic Hybrid Nanowires for Fast Ambipolar Charge Transport.

Donor-acceptor interfacial microstructures and fast ambipolar charge transport are pivotal in determining the device performance of inorganic-organic hybrid photovoltaics. Here, we report on a series of one-dimensional coaxial p-n junction core-shell nanohybrids formed by direct side-on attachment of carboxylated poly(3-alkylthiophene)s onto single-crystalline ZnO nanowires. The diameter of pristine ZnO nanowires is ∼30 nm, and the conjugated polymer forms a 2-10 nm shell around each nanowire.