High-Throughput Experimentation, Theoretical Modeling, and Human Intuition: Lessons Learned in Metal-Organic-Framework-Supported Catalyst Design.

We have screened an array of 23 metals deposited onto the metal-organic framework (MOF) NU-1000 for propyne dimerization to hexadienes. By a first-of-its-kind study utilizing data-driven algorithms and high-throughput experimentation (HTE) in MOF catalysis, yields on Cu-deposited NU-1000 were improved from 0.4 to 24.

Sulfated Zirconium Metal-Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis.

Understanding heterogeneous catalysts is a challenging pursuit due to surface site nonuniformity and aperiodicity in traditionally used materials. One example is sulfated metal oxides, which function as highly active catalysts and as supports for organometallic complexes. These applications are due to traits such as acidity, ability to act as a weakly coordinating ligand, and aptitude for promoting transformations via radical cation intermediates.

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization.

A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour.

Postsynthetically Modified Polymers of Intrinsic Microporosity (PIMs) for Capturing Toxic Gases.

Polymers of intrinsic microporosity (PIMs) are promising materials for gas adsorption because of their high surface area, processability, and tailorable backbone. Specifically, nitrile groups on the backbone of PIM-1, an archetypal PIM, can be converted to other functional groups to selectively capture targeted gas molecules. Despite these appealing features of PIMs, their potential has mainly only been realized for the separation of nontoxic gases.

Structural Diversity of Zirconium Metal-Organic Frameworks and Effect on Adsorption of Toxic Chemicals.

While linkers with various conformations pose challenges in the design and prediction of metal-organic framework (MOF) structures, they ultimately provide great opportunities for the discovery of novel structures thereby enriching structural diversity. Tetratopic carboxylate linkers, for example, have been widely used in the formation of Zr-based MOFs due to the ability to target diverse topologies, providing a promising platform to explore their mechanisms of formation. However, it remains a challenge to control the resulting structures when considering the complex assembly of linkers with unpredicted conformations and diverse Zr node connectivities.

Benign Integration of a Zn-Azolate Metal-Organic Framework onto Textile Fiber for Ammonia Capture.

Ammonia (NH) exposure has a serious impact on human health because of its toxic and corrosive nature. Therefore, efficient personal protective equipment (PPE) such as masks is necessary to eliminate and mitigate NH exposure risks. Because economically and environmentally viable conditions are of interest for large-scale manufacture of PPE, we herein report a benign procedure to synthesize a Zn-azolate metal-organic framework (MOF), MFU-4, for NH capture.

Metal-organic framework (MOF) materials as polymerization catalysts: a review and recent advances.

Synthetic polymers are ubiquitous across both the industrial and consumer segments of the world economy. Catalysts enable rapid, efficient, selective, and even stereoselective, formation of desired polymers from any of a host of candidate monomers. While numerous molecular catalysts have been shown to be effective for these reactions, separation of the catalysts from reaction products is typically difficult - a potentially problematic complication that suggests instead the use of heterogeneous catalysts.

Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid.

We report the performance of UiO-66 and its Brønsted acid functionalized derivative, UiO-66-(COOH), as heterogeneous catalysts for levulinic acid esterification with ethanol. Importantly, compared with UiO-66, UiO-66-(COOH) displayed superior catalytic performance (up to 97.0 ± 1.