Support effect in high activity gold catalysts for CO oxidation

In this work, we present a detailed study concerning the evaluation of the metal-support interaction in high activity gold catalysts for CO oxidation. Using the colloidal deposition method, model catalysts were prepared, which allow the isolation of the effect of the support on the catalytic activity. Prefabricated gold particles were thus deposited on different support materials. Since the deposition process did not change the particle sizes of the gold particles, only the influence of the support could be studied. TiO2, Al2O3, ZrO2, and ZnO were used as support materials. Catalytic tests and high resolution transmission electron microscopy clearly show that the support contributes to the activity. However, our results are not in line with the distinction between active and passive supports based on the semiconducting properties of the oxidic material. The most active catalysts were obtained with TiO2 and Al2O3, while ZnO and ZrO2 gave substantially less active catalysts. Furthermore, the effect of other important parameters on the catalytic activity (i.e., particles size distribution, calcination temperature, and aging time for a Au/TiO2 catalyst) has also been studied. Using this preparation route, the catalysts show high-temperature stability, size dependent activity, and a very good long-term stability.     

Chromogenic oxazines for cyanide detection

[reaction: see text] We have designed two heterocyclic compounds for the colorimetric detection of cyanide. The skeleton of both molecules fuses a benzooxazine ring to an indoline fragment and can be assembled efficiently in three synthetic steps starting from commercial precursors. The two compounds differ in the nature of the substituent on the carbon atom at the junction of the fused heterocycles, which can be either a methyl or a phenyl group. In the presence of cyanide, both molecules are converted quantitatively into cyanoamines with the concomitant appearance of an intense band in the visible region of the absorption spectrum. The developing absorption is a result of the opening of the benzooxazine ring with the formation of a 4-nitrophenylazophenolate chromophore. Nuclear magnetic resonance spectroscopy and X-ray crystallographic analyses demonstrate that the covalent attachment of a cyanide anion to the indoline fragment is responsible for these transformations. The chromogenic process is particularly fast for the methyl-substituted oxazine and can be exploited to detect micromolar concentrations of cyanide in water. Furthermore, the colorimetric response of this compound to cyanide does not suffer the interference of the halide anions, which instead are known to complicate the detection of cyanide in conventional sensing protocols. Thus, our mechanism and compounds for the colorimetric identification of cyanide can lead to the development of practical strategies for the convenient determination of this toxic anion in aqueous environments.     

Equivalent birational embeddings

Let X be a projective variety of dimension r over an algebraicallyclosed field. It is proven that two birational embeddings ofX in ⁿ with n r + 2 are equivalent up to Cremona transformationsof ⁿ.     

Evolved gas analysis (EGA) in TG and DSC with single photon ionisation mass spectrometry (SPI-MS): molecular organic signatures from pyrolysis of soft and hard wood,coal, crude oil and ABS polymer

A combined thermogravimetry/differential scanning calorimetry device (TG/DSC) was coupled to single photon ionisation mass spectrometry (SPI-MS) for evolved gas analysis (EGA). Single photon ionisation (SPI) was performed with a new type of VUV light source, the so called electron beam pumped rare gas excimer lamp (EBEL). SPI does not fragment molecules upon the ionisation process. Thus the molecular mass signature of the evolving gases from thermal composition of carbonaceous material can be directly on-line recorded. In this work the thermo-analytical data and the SPI-MS information on the released organics is presented and discussed for various samples. Namely biomass (soft and hard wood), fossil fuel (crude oil and coal) as well as a complex polymer (ABS) are investigated. The general potential of hyphenating thermal analysis and soft photo ionisation mass spectrometry (EBEL-SPI-MS) for fundamental and applied research and material analysis is discussed.     

Methoxy‐ether and crown‐ether ­derivatives of tetrahomodioxa‐ and octahomotetraoxacalix­[4]­arenes

Three methoxy­‐ether and one methoxy‐­ether/crown‐ether derivatives of p‐tert‐butyl­tetrahomodioxa‐ and p‐R‐octahomo­tetraoxacalix­[4]­arenes (R = methyl, tert‐butyl, H) have been investigated. The first three compounds, 7,15,21,27‐tetra‐tert‐butyl‐29,30,31,32‐tetra­methoxy‐3,11‐dioxapenta­cyclo­[23.3.­1.1^5,9.1^13,17.1^19,23]­ditriaconta‐1(29),5,7,­9(30),­13,15,‐17(31),­19,21,23(32),25,27‐dodecaene, C₅₀H₆₈O₆, 33,34,35,36‐tetra­methoxy‐7,15,23,31‐tetra­methyl‐3,11,19,27‐tetra­oxa­penta­cyclo[27.3.1.1^5,9.1^13,17.1^21,25]­hexa­tri­aconta‐1(33),5,7,9(34),13,15,­17(35),21,23,25(36),29,31‐dodecaene, C₄₀H₄₈O₈, and 7,23‐di‐tert‐butyl‐33,34,35,36‐tetra­methoxy‐3,11,19,27‐tetraoxapenta­cyclo­[27.3.1.1^5,9.1^13,17.1^21,25]­hexatriaconta‐1(33),5,7,9(34),13,15,­17(35),‐ 21,23,25(36),29,31‐dodecaene, C₄₄H₅₆O₈, in the partial‐cone or 1,2‐alternate conformations, present the common feature of methoxy‐­ether self‐inclusion, while the fourth, 42,43‐di­methoxy‐7,15,23,31‐tetra­methyl‐3,11,19,27,34,37,40‐heptaoxahexa­cyclo[15.15.9.1^5,9.1^21,25.0^13,41.0^29,33]­tritetra­conta‐5(42),6,8,13(41),­14,16,21(43),22,24,29(33),30,32‐dodecaene, C₄₂H₅₀O₉, adopts the 1,3‐alternate conformation owing to the presence of a 1,3‐polyether chain.     

Algorithmic Approaches for Assessing Irreversibility in Time Series: Review and Comparison

The assessment of time irreversibility, i.e., of the lack of invariance of the statistical properties of a system under the operation of time reversal, is a topic steadily gaining attention within the research community. Irreversible dynamics have been found in many real-world systems, with alterations being connected to, for instance, pathologies in the human brain, heart and gait, or to inefficiencies in financial markets. Assessing irreversibility in time series is not an easy task, due to its many aetiologies and to the different ways it manifests in data. It is thus not surprising that several numerical methods have been proposed in the last decades, based on different principles and with different applications in mind. In this contribution we review the most important algorithmic solutions that have been proposed to test the irreversibility of time series, their underlying hypotheses, computational and practical limitations, and their comparative performance. We further provide an open-source software library that includes all tests here considered. As a final point, we show that “one size does not fit all”, as tests yield complementary, and sometimes conflicting views to the problem; and discuss some future research avenues.     

LSb(μ‐I)2(μ‐S)SbL: a Neutral Triply Bridged Complex obtained from Sb Powder and Diiodine activated by Tetraphenyldithioimidodiphosphine (HL)

The synthesis of the complex LSb(μ‐I)₂(μ‐S)SbL ( 1 ) was accomplished by reacting antimony powder with diiodine activated by tetraphenyldithioimidodiphosphine (SPPh₂NHPPh₂S) (H L ). X‐ray diffraction (tetragonal, M = 1426.30, space group I 4₁/a (No. 88), Z = 8, a = 18.020(2) Å, c = 33.037(4) Å) shows that ( 1 ) is a dinuclear Sb^III complex, in which the two metal ions are bridged by one sulphide and two iodide anions. An anionic bidentate L ligand completes the coordination sphere of each metal with its two sulphur atoms, leading to a slightly distorted pyramidal coordination geometry, since each metal ion shows the presence of a sterically active lone‐pair in trans position to the bridging sulphide. ³¹P CP‐MAS NMR and IR spectroscopies are in accordance with the structural features of the complex.     

Vibrational Energy Transfer in CO+N2 Collisions: A Database for V–V and V–T/R Quantum-Classical Rate Coefficients

Knowledge of energy exchange rate constants in inelastic collisions is critically required for accurate characterization and simulation of several processes in gaseous environments, including planetary atmospheres, plasma, combustion, etc. Determination of these rate constants requires accurate potential energy surfaces (PESs) that describe in detail the full interaction region space and the use of collision dynamics methods capable of including the most relevant quantum effects. In this work, we produce an extensive collection of vibration-to-vibration (V–V) and vibration-to-translation/rotation (V–T/R) energy transfer rate coefficients for collisions between CO and N2 molecules using a mixed quantum-classical method and a recently introduced (A. Lombardi, F. Pirani, M. Bartolomei, C. Coletti, and A. Laganà, Frontiers in chemistry, 7, 309 (2019)) analytical PES, critically revised to improve its performance against ab initio and experimental data of different sources. The present database gives a good agreement with available experimental values of V–V rate coefficients and covers an unprecedented number of transitions and a wide range of temperatures. Furthermore, this is the first database of V–T/R rate coefficients for the title collisions. These processes are shown to often be the most probable ones at high temperatures and/or for highly excited molecules, such conditions being relevant in the modeling of hypersonic flows, plasma, and aerospace applications.     

Enriching the Finite Element Method with meshfree techniques in structural mechanics

The automatic generation of meshes for the Finite Element method can be an expensive computational burden, especially in structural problems with localized stress peaks. The use of meshless methods can address such an issue, as these techniques do not require the existence of an underlying connection among the nodes selected in a general domain. However, a thoroughly meshfree technique can be computationally quite expensive. Usually, the most expensive tasks rely on identifying the nodal contacts and computing the Galerkin integrals. In this thesis we advance a novel hybrid technique that blends Finite Elements with the Meshless Local Petrov-Galerkin method with the aim at exploiting the most attractive properties of each procedure. The idea relies on the use of the Finite Element Method to compute a background solution that is locally improved by enriching the approximating space with the basis functions associated to a few meshless nodes, thus taking advantage of the flexibility ensured by the use of particles disconnected from an underlying grid. Adding the meshless particles only where needed avoids the cost of mesh refining, or even of re-meshing, without the prohibitive burden of a thoroughly meshfree approach. In particular, two enriching methods are introduced and discussed, with applications in structural mechanics. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)