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.     

Connected Domatic Number in Planar Graphs

A dominating set in a graph G is a connected dominating set of G if it induces a connected subgraph of G. The connected domatic number of G is the maximum number of pairwise disjoint, connected dominating sets in V(G). We establish a sharp lower bound on the number of edges in a connected graph with a given order and given connected domatic number. We also show that a planar graph has connected domatic number at most 4 and give a characterization of planar graphs having connected domatic number 3.     

The design of Helmholtz resonator based acoustic lenses by using the symmetric Multi-Level Wave Based Method and genetic algorithms

Sonic crystals can be used as acoustic lenses in certain frequencies and the design of such systems by creating vacancies and using genetic algorithms has been proven to be an effective method. So far, rigid cylinders have been used to create such acoustic lens designs. On the other hand, it has been proven that Helmholtz resonators can be used to construct acoustic lenses with higher refraction index as compared to rigid cylinders, especially in low frequencies by utilizing their local resonances. In this paper, these two concepts are combined to design acoustic lenses that are based on Helmholtz resonators. The Multi-Level Wave Based Method is used as the prediction method. The benefits of the method in the context of design procedure are demonstrated. In addition, symmetric boundary conditions are derived for more efficient calculations. The acoustic lens designs that use Helmholtz resonators are compared with the acoustic lens designs that use rigid cylinders. It is shown that using Helmholtz resonator based sonic crystals leads to better acoustic lens designs, especially at the low frequencies where the local resonances are pronounced.     

Five-torsion in the homology of the matching complex on 14 vertices

J.L. Andersen proved that there is 5-torsion in the bottom nonvanishing homology group of the simplicial complex of graphs of degree at most two on seven vertices. We use this result to demonstrate that there is 5-torsion also in the bottom nonvanishing homology group of the matching complex on 14 vertices. Combining our observation with results due to Bouc and to Shareshian and Wachs, we conclude that the case n=14 is exceptional; for all other n, the torsion subgroup of the bottom nonvanishing homology group has exponent three or is zero. The possibility remains that there is other torsion than 3-torsion in higher-degree homology groups of when n≥13 and n≠14. Research of J. Jonsson was supported by European Graduate Program “Combinatorics, Geometry, and Computation”, DFG-GRK 588/2.     

Exact sequences for the homology of the matching complex

Building on work by Bouc and by Shareshian and Wachs, we provide a toolbox of long exact sequences for the reduced simplicial homology of the matching complex Mn, which is the simplicial complex of matchings in the complete graph Kn. Combining these sequences in different ways, we prove several results about the 3-torsion part of the homology of Mn. First, we demonstrate that there is nonvanishing 3-torsion in whenever , where . By results due to Bouc and to Shareshian and Wachs, is a nontrivial elementary 3-group for almost all n and the bottom nonvanishing homology group of Mn for all n≠2. Second, we prove that is a nontrivial 3-group whenever . Third, for each k?0, we show that there is a polynomial fk(r) of degree 3k such that the dimension of , viewed as a vector space over Z₃, is at most fk(r) for all r?k+2.     

Structure and mobility of lipid membranes on a thermoplastic substrate

Supported lipid membranes constitute one of the most important model systems for cell membranes. The properties of lipid membranes supported by the hydrophobic solid polymer cyclic olefin copolymer (COC) were investigated. Lipid layers consisting of varying amounts of 1,2-dioleoyl-3-trimethylammonium propane (DOTAP, cationic) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC, neutral) prepared by vesicle fusion and solvent exchange were compared. All lipid mixtures coated the COC surface homogeneously forming a fluid membrane as verified by fluorescence microscopy and fluorescence recovery after photobleaching (FRAP). The exact structure of the supported membranes was determined by synchrotron reflectivity experiments using a microfluidic chamber. The X-ray data are in agreement with a compressed (head-to-head distance = 29 angstroms) and less densely packed bilayer.     

Predicting catalysis: understanding ammonia synthesis from first-principles calculations

Here, we give a full account of a large collaborative effort toward an atomic-scale understanding of modern industrial ammonia production over ruthenium catalysts. We show that overall rates of ammonia production can be determined by applying various levels of theory (including transition state theory with or without tunneling corrections, and quantum dynamics) to a range of relevant elementary reaction steps, such as N(2) dissociation, H(2) dissociation, and hydrogenation of the intermediate reactants. A complete kinetic model based on the most relevant elementary steps can be established for any given point along an industrial reactor, and the kinetic results can be integrated over the catalyst bed to determine the industrial reactor yield. We find that, given the present uncertainties, the rate of ammonia production is well-determined directly from our atomic-scale calculations. Furthermore, our studies provide new insight into several related fields, for instance, gas-phase and electrochemical ammonia synthesis. The success of predicting the outcome of a catalytic reaction from first-principles calculations supports our point of view that, in the future, theory will be a fully integrated tool in the search for the next generation of catalysts.     

Destructive adsorption of CCl4 over lanthanum-based solids: linking activity to acid-base properties

The relative activities of a low-surface crystalline and high-surface amorphous LaOCl, further denoted as S1 and S2, have been compared for the destructive adsorption of CCl4. It was found that the intrinsic activity of S2 is higher than that of S1. Both samples were characterized with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2-physisorption, and Raman and infrared (IR) spectroscopy. IR was used in combination with CO2, CO, and methanol as probe molecules. The CO2 experiments showed that different carbonate species are formed on both materials. For S1, a high surface concentration of bidentate carbonate species and a lower concentration of monodentate carbonate were observed. In the case of S2, bulk carbonates were present together with bridged carbonates. CO adsorption shows that S2 and S1 have very similar Lewis acid sites. However, methanol adsorption experiments showed that S2 had a higher number of stronger Lewis acid sites than S1 and that twofold coordinated methoxy species were more strongly bound than threefold coordinated methoxy species. Because of the analogy between methanol dissociation and the removal of the first chlorine atom in the destructive adsorption of CCl4, the sites enabling twofold coordination were likely to be the same Lewis acid sites actively involved in the destructive adsorption of CCl4. La2O3 was less active than the two LaOCl materials, and therefore, the intrinsic activity of the catalyst increases as the strength of the Lewis acid sites increases. S2 contains more chlorine at the surface than S1, which is expressed by the higher number of sites enabling twofold coordination. Moreover, this explains the difference in destructive adsorption capacity for CCl4 that was observed for the samples S1 and S2. Since LaCl3, being the most acidic phase, is not active for the destructive adsorption of CCl4, basic oxygen atoms, however, remain needed to stabilize the reaction intermediate CCl3 as La-O-CCl3.