Revisiting the Incorporation of Ti(IV) in UiO-type Metal–Organic Frameworks: Metal Exchange versus Grafting and Their Implications on Photocatalysis

Revisiting the Incorporation of Ti(IV) in UiO-type Metal–Organic Frameworks: Metal Exchange versus Grafting and Their Implications on Photocatalysi

Crystal structure of 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid dihydrate, C14H16N2O6

C14H16N2O6, triclinic, P1̅ (no. 2), a = 10.0254(5) Å, b = 11.2726(6) Å, c = 13.4494(7) Å, α = 111.535(2)°, β = 92.068(2)°, γ = 102.644(2)°, V = 1368.16(13) Å3, Z = 4, Rgt(F) = 0.047, wRref(F2) = 0.133, T = 150 K.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007–2013) / ERC Grant Agreement No.335746, CrystEngMOF-MMM. S. G.-G. thanks to Ministerio de Economía y Competitividad, MAT2013-40950-R, for financial support.Peer Reviewe

Rh-Mediated C1-Polymerization: Copolymers from Diazoesters and Sulfoxonium Ylides

In this paper, we present new results obtained in our investigations of Rh-catalyzed C1 (co)­polymerization reactions using carbene units as monomers. We demonstrate here, for the first time, the use of transition metal catalysts in carbene polymerization using sulfur ylides as the carbene monomer precursors. Furthermore, we show that it is possible to generate unique diblock copolymers from sulfoxonium ylides and diazoesters as the respective carbene monomer precursors. This constitutes an entirely new approach to the synthesis of functional copolymers. The copolymerization reactions were successful, and high-<i>M</i>_w poly­(methylene)-poly­(ester carbene) copolymers were obtained with a diblock-syndiotactic microstructure in decent yields. These copolymers can be used as blending agents to mix polyethylene or polymethylene with poly­(ethyl 2-ylidene-acetate). The copolymer properties are highly dependent on the functional-group content. Model studies and investigations on the influence of the catalyst structure on the obtained polymer yields provide insights into the catalyst activation and deactivation processes operative under the applied reaction conditions

Manufacture of highly loaded silica-supported cobalt Fischer–Tropsch catalysts from a metal organic framework

Preparation of supported catalysts with high nanoparticle loading is a considerable synthetic challenge. Here, by using a metal organic framework as sacrificial template, the authors report a cobalt catalyst with a 50% Co loading with superior activity in the C5+ selective production of hydrocarbons from syngas

Facile Method for the Preparation of Covalent Triazine Framework coated Monoliths as Catalyst Support: Applications in C1 Catalysis

A quasi chemical vapor deposition method for the manufacture of well-defined covalent triazine framework (CTF) coatings on cordierite monoliths is reported. The resulting supported porous organic polymer is an excellent support for the immobilization of two different homogeneous catalysts: (1) an Ir^IIICp*-based catalyst for the hydrogen production from formic acid and (2) a Pt^II-based catalyst for the direct activation of methane via Periana chemistry. The immobilized catalysts display a much higher activity in comparison with the unsupported CTF operated in slurry because of improved mass transport. Our results demonstrate that CTF-based catalysts can be further optimized by engineering at different length scales

Isolated Fe Sites in Metal Organic Frameworks Catalyze the Direct Conversion of Methane to Methanol

Hybrid materials bearing organic and inorganic motifs have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal metal organic framework (MOF) that mimics the reactivity of soluble methane monooxygenase enzyme and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterization of an Fe-containing MOF that comprises the desired antiferromagnetically coupled high-spin species in a coordination environment closely resembling that of the enzyme. An electrochemical synthesis method is used to build the microporous MOF matrix while integrating the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C–H activation behavior of the enzyme to produce methanol and shows that the key to this reactivity is the formation of isolated oxo-bridged Fe units