Nanoweb Surface-Mounted Metal–Organic Framework Films with Tunable Amounts of Acid Sites as Tailored Catalysts

Metal–organic frameworks (MOFs) are a promising class of materials for many applications, due to their high chemical tunability and superb porosity. By growing MOFs as (thin-)films, additional properties and potential applications become available. Here, copper (II) 1,3,5-benzenetricarboxylate (Cu-BTC) metal–organic framework (MOF) thin-films are reported, which were synthesized by spin-coating, resulting in “nanowebs”, that is, fiber-like structures. These surface-mounted MOFs (SURMOFs) were studied by using photoinduced force microscopy (PiFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The optimal concentration of precursors (10 mm ) was determined that resulted in chemically homogeneous, pure nanowebs. Furthermore, the morphology and (un)coordinated Cu sites in the web were tuned by varying the rotation speed of the spin-coating process. X-ray diffraction (XRD) analysis showed that rotation speeds ≥2000 rpm (with precursors in a water/ethanol solution) generate the catena-triaqua-μ-(1,3,5-benzenetricarboxylate)-copper(II), or Cu(BTC)(H₂O)₃ coordination polymer. X-ray photoelectron spectroscopy (XPS) highlighted the strong decrease in number of (defective) Cu⁺ sites, as the nanowebs mainly consist of coordinated Cu²⁺ Lewis acid sites (LAS) and organic linker–linker, for example, hydrogen-bonding, interactions. Finally, the Lewis-acidic character of the Cu sites is illustrated by testing the films as catalysts in the isomerization of α-pinene oxide. The higher number of LAS (≥3000 rpm), result in higher campholenic aldehyde selectivity reaching up to 87.7 %. Furthermore, the strength of a combined micro- and spectroscopic approach in understanding the nature of MOF thin-films in a spatially resolved manner is highlighted.     

Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism

The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd⁰(PPh₃)₂] (generated from [Pd⁰(PPh₃)₄]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2‐halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented S_NAr‐type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies.     

A versatile A2 + B3 approach to hyperbranched polyacenaphthenequinones

A series of hyperbranched polyacenaphthenequinones has been prepared by superelectrophilic aromatic substitution of (substituted) acenaphthenequinone and 1,3,5‐tris‐(4‐phenoxybenzoyl)benzene via a facile A₂ + B₃ approach. Because of the strongly increased reactivity of the second A functionality, gelation was efficiently avoided during the polymerization. The structure of the resulting polymer was characterized by NMR spectroscopy and gel permeation chromatography. Further modification of the hyperbranched polyacenaphthenequinone was explored both on the acenaphthenequinone and aromatic moieties. Moreover, the polymer modified through sulfonation was investigated as a water‐soluble acid catalyst for the degradation of biomass resources. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2596‐2603     

On the genericity of loxodromic actions

Suppose that a finitely generated group G acts by isometries on a δ-hyperbolic space, with at least one element acting loxodromically. Suppose that the elements of G have a normal form such that the language of normal forms can be recognized by a finite state automaton. Suppose also that a certain compatibility condition linking the automatic and the δ-hyperbolic structures is satisfied. Then we prove that in the “ball” consisting of elements of G whose normal form is of length at most l, the proportion of elements which act loxodromically is bounded away from zero, as l tends to infinity. We present several applications of this result, including the genericity of pseudo-Anosov braids.     

Curve graphs and Garside groups

We present a simple construction which associates to every Garside group a metric space, called the additional length graph, on which the group acts. These spaces share important features with curve graphs: they are \(\delta \)-hyperbolic, infinite, and typically locally infinite graphs. We conjecture that, apart from obvious counterexamples, additional length graphs have always infinite diameter. We prove this conjecture for the classical example of braid groups \((B_n,B_n^{+},\varDelta )\); moreover, in this framework, reducible and periodic braids act elliptically, and at least some pseudo-Anosov braids act loxodromically. We conjecture that for \(B_n\), the additional length graph is actually quasi-isometric to the curve graph of the n times punctured disk.     

High‐Resolution Single‐Molecule Fluorescence Imaging of Zeolite Aggregates within Real‐Life Fluid Catalytic Cracking Particles

Fluid catalytic cracking (FCC) is a major process in oil refineries to produce gasoline and base chemicals from crude oil fractions. The spatial distribution and acidity of zeolite aggregates embedded within the 50–150 μm‐sized FCC spheres heavily influence their catalytic performance. Single‐molecule fluorescence‐based imaging methods, namely nanometer accuracy by stochastic chemical reactions (NASCA) and super‐resolution optical fluctuation imaging (SOFI) were used to study the catalytic activity of sub‐micrometer zeolite ZSM‐5 domains within real‐life FCC catalyst particles. The formation of fluorescent product molecules taking place at Brønsted acid sites was monitored with single turnover sensitivity and high spatiotemporal resolution, providing detailed insight in dispersion and catalytic activity of zeolite ZSM‐5 aggregates. The results point towards substantial differences in turnover frequencies between the zeolite aggregates, revealing significant intraparticle heterogeneities in Brønsted reactivity.     

Subgrid-modelling in LES of compressible flow

Subgrid-models for Large Eddy Simulation (LES) of compressible turbulent flow are tested for the three-dimensional mixing layer. For the turbulent stress tensor the recently developed dynamic mixed model yields reasonable results.A priori estimates of the subgrid-terms in the filtered energy equation show that the usually neglected pressure-dilatation and turbulent dissipation rate are as large as the commonly retained pressure-velocity subgrid-term. Models for all these terms are proposed: a similarity model for the pressure-dilatation, similarity andk-dependent models for the turbulent dissipation rate and a dynamic mixed model for the pressure-velocity subgrid-term. Actual LES demonstrates that for a low Mach number all subgrid-terms in the energy equation can be neglected, while for a moderate Mach number the effect of the modelled turbulent dissipation rate is larger than the combined effect of the other modelled subgrid-terms in the filtered energy equation.