A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation

Direct selective oxidation of hydrocarbons to oxygenates by O₂ is challenging. Catalysts are limited by the low activity and narrow application scope, and the main focus is on active C−H bonds at benzylic positions. In this work, stable, lead-free, Cs₃Bi₂Br₉ halide perovskites are integrated within the pore channels of mesoporous SBA-15 silica and demonstrate their photocatalytic potentials for C−H bond activation. The composite photocatalysts can effectively oxidize hydrocarbons (C₅ to C₁₆ including aromatic and aliphatic alkanes) with a conversion rate up to 32900 μmol g_cat⁻¹ h⁻¹ and excellent selectivity (>99 %) towards aldehydes and ketones under visible-light irradiation. Isotopic labeling, in situ spectroscopic studies, and DFT calculations reveal that well-dispersed small perovskite nanoparticles (2–5 nm) possess enhanced electron–hole separation and a close contact with hydrocarbons that facilitates C(sp³)−H bond activation by photoinduced charges.     

Possible use of DFT approaches for the determination of double exchange interactions

DFT calculations are performed on a model mixed-valence system presenting a double exchange phenomenon. Due to the intrinsic multireference character of the lowest Ms components of the spin states, it is shown that the interactions involved in the double-exchange model cannot be simply extracted from the DFT energies as it is sometimes done. It is, however, possible to extract from different DFT single determinant energies the interactions of a generalized Hubbard Hamiltonian, from which, in a second step, the double-exchange spectrum may be evaluated. The problems generated by the charge and spin polarization are discussed in both symmetric and non symmetric geometries, and the sensitivity of the results to the choice of the density functional is illustrated.     

Suppressed compressibility at large scale in jammed packings of size-disperse spheres

We analyze the large-scale structure and fluctuations of jammed packings of size-disperse spheres, produced in a granular experiment as well as numerically. While the structure factor of the packings reveals no unusual behavior for small wave vectors, the compressibility displays an anomalous linear dependence at low wave vectors and vanishes when q→0. We show that such behavior occurs because jammed packings of size-disperse spheres have no bulk fluctuations of the volume fraction and are thus hyperuniform, a property not observed experimentally before. Our results apply to arbitrary particle size distributions. For continuous distributions, we derive a perturbative expression for the compressibility that is accurate for polydispersity up to about 30%.     

Kreiss symmetrizer and boundary conditions for the Euler-Korteweg system in a half space

The Euler-Korteweg system is a third order, dispersive system of PDEs, obtained from the standard Euler equations for compressible fluids by adding the so-called Korteweg stress tensor - encoding capillarity effects. Various results of well-posedness have been obtained recently for the Cauchy problem associated with the Euler-Korteweg system in the whole space. As to mixed problems, with initial and boundary value data, they are still mostly open. Here the linearized Euler-Korteweg system is studied in a half space by the use of normal mode analysis, which yields a generalized Kreiss-Lopatinski? condition that must be satisfied by the boundary conditions for the boundary value problem to be well-posed.Conversely, under the uniform Kreiss-Lopatinski? condition, generalized Kreiss symmetrizers are constructed in one space dimension for an extended system originally introduced for the Cauchy problem, which displays crucial quasi-homogeneity properties. A priori estimates without loss of derivatives are thus derived, and finally the well-posedness of the mixed problem is obtained by combining the estimates for the pure boundary value problem and trace results for solutions of the pure Cauchy problem.     

Monitoring the Light-induced Isomerisation of the Prototypical Polycyclic Aromatic Hydrocarbons C10H8+ through Ion-Molecule Reactions

Structural rearrangements in ions are essential for understanding the composition and evolution of energetic and chemically active environments. This study explores the interconversion routes for simple polycyclic aromatic hydrocarbons, namely naphthalene and azulene radical cations (C₁₀H₈⁺), by combining mass spectrometry and vacuum ultraviolet tunable synchrotron radiation through the chemical monitoring technique. Products of ion-molecule reactions are used to probe C₁₀H₈⁺ structures that are formed as a function of their internal energies. Isomerisation from azulene radical cation towards naphthalene radical cation in a timescale faster than 80 μs was monitored, whereas no reverse isomerisation was observed in the same time window. When energising C₁₀H₈⁺ with more than 6 eV, the reactivity of C₁₀H₈⁺ unveils the formation of a new isomeric group with a contrasted reactivity compared with naphthalene and azulene cations. We tentatively assigned these structures to phenylvinylacetylene cations.     

A Mordell-Lang plus Bogomolov type result for curves in \mathbbGm2{\mathbb{G}_{m}^{2}}

We prove a sharper so-called Mordell-Lang plus Bogomolov type result for curves lying in the two-dimensional linear torus. We mainly follow the approach of Rémond in (Comp Math 134:337–366, 2002), using Vojta and Mumford type inequalities. In the special case we consider, we improve Rémond’s main result using a better Bogomolov property and an elementary arithmetic Bézout theorem.     

Simulation and data reconstruction for NDT phased array techniques

Phased array techniques are now widely employed for industrial NDT applications in various contexts. Indeed, phased array present a great adaptability to the inspection configuration and the application of suitable delay laws allows to optimize the detection and characterization performances by taking into account the component geometry, the material characteristics, and the aim of the inspection. In addition, the amount of potential information issued from the inspection is in general greatly enhanced. It is the case when the employed method involve sequences of shots (sectorial scanning, multiple depth focusing etc) or when signals received on the different channels are stored. At last, application of electronic commutation make possible higher acquisition rates. Accompanying these advantages, it is clear that an optimal use of such techniques require the application of simulation-based algorithms at the different stages of the inspection process: When designing the probe by optimizing number and characteristics of element; When conceiving the inspection method by selecting suitable sequences of shots, computing optimized delay laws and evaluating the performances of the control in terms of zone coverage or flaw detection capabilities; When analysing the results by applying simulation-helped visualization and data reconstruction algorithms. For many years the CEA (French Atomic Energy Commission) has been being greatly involved in the development of such phased arrays simulation-based tools. In this paper, we will present recent advances of this activity and show different examples of application carried out on complex situations.     

Studying Natural Buckyballs and Buckybowls in Fossil Materials

Buckyballs (fullerenes) were first reported over 30 years ago, but still little is known regarding their natural occurrence, since they have so far only been found at sites of high‐energy incidents, such as lightning strikes or meteor impacts, but have not been reported in low‐energy materials like fossil fuels. Using ultrahigh‐resolution mass spectrometry, a wide range of fullerenes from C₃₀ to C₁₁₄ was detected in the asphaltene fraction of a heavy crude oil, together with their building blocks of C_10nH₁₀ stoichiometry. High‐level DLPNO‐CCSD(T) calculations corroborate their stability as spherical and hemispherical species. Interestingly, the maximum intensity of the fullerenes was found at C₄₀ instead of the major fullerene C₆₀. Hence, experimental evidence supported by calculations show the existence of not only buckyballs but also buckybowls as 3‐dimensional polyaromatic compounds in fossil materials.     

Direct Synthesis of Allyl Amines with 2-Nitrosulfonamide Derivatives via the Tsuji-Trost Reaction

The Tsuji-Trost Reaction is a palladium-catalysed allylation of nucleophiles that consists in the reaction of a nitrogen, carbon or oxygen-based nucleophiles with an allylic substrate bearing a leaving group. Here we present the use of 2-nitrosulfonamide derivatives as nucleophile, which are reactive under mild conditions. 2-nitrosulfonyl groups are well-known dual protective activator groups easy to introduce in any type of amine substrates. The resulting 2-nitrosulfonamide derivatives are ideal substrates for the Tsuji-Trost reaction to afford a convenient and flexible access to primary and dissymmetric secondary allyl amines. The optimised procedure is flexible (for solvent, temperature, functional groups) and has been applied with good to excellent yield to access to a wide range of allyl amine derivatives.