Al-RUB-41: a shape-selective zeolite catalyst from a layered silicate

A new zeolite catalyst, Al-RUB-41, was synthesized for the first time. It was tested as a catalyst in methanol amination, and showed a shape-selective performance that results in a highly favorable product distribution. The shape-selective nature was also evidenced by using Pt-Al-RUB-41 as a bifunctional catalyst for decane hydroconversion. With its unique pore architecture and remarkable shape-selective character, Al-RUB-41 presents a significant commercial potential in industrial catalysis.     

Concentration-Dependent Seeding as a Strategy for Fabrication of Densely Packed Surface-Mounted Metal–Organic Frameworks (SURMOF) Layers

The layer-by-layer (LbL) method is a well-established method for the growth of surface-attached metal–organic frameworks (SURMOFs). Various experimental parameters, such as surface functionalization or temperature, have been identified as essential in the past. In this study, inspired by these recent insights regarding the LbL SURMOF growth mechanism, the impact of reactant solutions concentration on LbL growth of the Cu₂(F₄bdc)₂(dabco) SURMOF (F₄bdc²⁻=tetrafluorobenzene-1,4-dicarboxylate and dabco=1,4-diazabicyclo-[2.2.2]octane) in situ by using quartz-crystal microbalance and ex situ with a combination of spectroscopic, diffraction and microscopy techniques was investigated. It was found that number, size, and morphology of MOF crystallites are strongly influenced by the reagent concentration. By adjusting the interplay of nucleation and growth, we were able to produce densely packed, yet thin films, which are highly desired for a variety of SURMOF applications.     

Electronic excitations during grazing scattering of hydrogen atoms on KI(001) and LiF(001) surfaces

The energy loss of hydrogen atoms with energies of 400 eV and 1 keV is studied in coincidence with the number of emitted electrons during grazing scattering from atomically clean and flat KI(001) and LiF(001) surfaces. The energy loss spectra for specific numbers of emitted electrons are analyzed in terms of a binary interaction model based on the formation of transient negative ions via local capture of valence band electrons from anion sites. Based on computer simulations we derive for this interaction scenario probabilities for the production of surface excitons, for electron loss to the conduction band of KI, for emission of electrons, and for formation of negative hydrogen ions. The pronounced differences of data obtained for the two surfaces are attributed to the different electronic structures of KI and LiF.     

Temperature dependence in the Schumann-Runge photoabsorption continuum of oxygen

The photoabsorption cross section in the Schumann-Runge continuum of oxygen has been measured with high precision over the wavelength region 140–174 nm at temperatures in the range 295–575 K. Models for the upper state potential and the electronic transition moment were used in the calculation of the cross section and its temperature dependence. By comparing this theoretical cross section with measured values, curves for the upper state potential and the transition moment in the continuum region have been obtained independently for the first time.     

Rotational variation of predissociation linewidths for the Schumann-Runge bands of molecular oxygen

Predissociation linewidths are presented as a function of rotation for the (3-0)-(14-0) Schumann- Runge bands of molecular oxygen. While there may be a slight tendency overall for the linewidths to increase with rotation, it is shown that previous assumptions of linewidths constant with rotation are generally valid within the experimental error for the range of rotation studied, N_n ? 21. There is no evidence for the sudden increase in linewidth with rotation reported elsewhere.     

Experimentally determined oscillator strengths and linewidths for the Schumann-Runge band system of molecular oxygen—I. The (6-0)–(14-0) bands

Experimental oscillator strengths and predissociated linewidths have been measured at room temperature for the (6-0)–(14-0) Schumann-Runge bands of molecular oxygen using the Adelaide 6 m vacuum u.v. monochromator operated at a resolution of about 0.06 Å. Photoelectric detectors were used to measure the u.v. absorption at two different gas pressures for 138 groups of rotational lines distributed throughout the (6-0)–(14-0) bands and the resulting data were interpreted using an equivalent width type of analysis. Experimental measurements of the variation with N″ of the oscillator strengths within each band have been obtained for the first time. Measured oscillator strengths are found to be somwhat higher in general than previously reported values with a slightly faster decrease as N″ increases than is predicted theoretically. The mean predissociated linewidths obtained for each band show a smooth variation with v′, agreeing well with other results for v′=12?14 and lying between previously reported experimental and theoretical values for v′=6?9. The present work provides results which can be used to construct highly accurate synthetic absorption profiles for studies of the atmospheric absorption of u.v. radiation by the Schumann-Runge bands.     

Casimir edge effects

We compute Casimir forces in open geometries with edges, involving parallel as well as perpendicular semi-infinite plates. We focus on Casimir configurations which are governed by a unique dimensional scaling law with a universal coefficient. With the aid of worldline numerics, we determine this coefficient for various geometries for the case of scalar-field fluctuations with Dirichlet boundary conditions. Our results facilitate an estimate of the systematic error induced by the edges of finite plates, for instance, in a standard parallel-plate experiment. The Casimir edge effects for this case can be reformulated as an increase of the effective area of the configuration.     

The substitution of germanium for silicon in AST-type zeolite

The substitution of silicon by germanium in the AST zeolite framework type, [Si_nGe_40−nO₈₀]*4(SDA⁺F⁻) expressed as unit cell content in its cubic F-centered symmetry, has been studied. Three different kinds of templates, dimethyldiethylammonium, dimethyldiisopropylammonium and isopropyltrimethylammonium cations, were used in the hydrothermal synthesis process in fluoride medium. The products were identified with XRD, MAS NMR, SEM and thermal analysis. The analysis of the X-ray powder diagrams shows that AST crystallizes in different space group symmetries depending on the nature of the SDA and the degree of Ge-substitution. The resonance signals of ¹⁹F in MAS NMR experiments for the pure Si- and Ge-end members are at −38.2 and −15 ppm, respectively, indicating that the F⁻-anion is located as co-template in the double-four-ring (D4R) of the tetrahedral framework. This is confirmed by Rietveld analysis of powder diffraction data of the pure Ge-end member. The peak splitting of the ¹⁹F NMR signal in pure GeO₂AST-type material is related to the displacement of F⁻ location inside the D4R. Two more distinct signals at −8 and −19 ppm, respectively, are observed for X-ray pure AST-samples of intermediate compositions and assigned to fluoride in D4R built of 4[GeO₄]- and 4[SiO₄]-tetrahedra (4Ge, 4Si) and to (2Ge, 6Si)-D4R, respectively. An ordered distribution of Ge in the AST-framework is proposed for cubic AST with compositions around Si/Ge=1.5–1 by correlating the intensities of ¹⁹F NMR signals and the results from chemical analysis. This model is further confirmed by the quantitative analyses of the corresponding ²⁹Si MAS NMR spectra.