Selective synthesis of alcohols from syngas and hydroformylation of ethylene over supported cluster-derived cobalt catalysts

Hydroformylation of ethylene and CO hydrogenation were studied over cobalt-based catalysts derived from reaction of Co₂(CO)₈ with ZnO, MgO and La₂O₃ supports. At 433 K a similar activity sequence was reached for both reactions: Co/ ZnO > Co/La₂O₃ > Co/MgO. This confirms the deep analogy between hydroformylation and CO hydrogenation into alcohols. In the CO hydrogenation the selectivity towards alcohol mixture (C₁-C₃) was found to be near 100% at 433 K for a conversion of 6% over the Co/ZnO catalyst; this catalyst showed oxo selectivity higher than 98% in the hydroformylation of ethylene. Magnetic experiments showed that no metallic cobalt particles were formed at 433 K. It is suggested that the active site for the step that is common to both reactions is related to the surface homonuclear Co²⁺/[Co(CO)₄]^– ion-pairing species.     

Modulation of Mechanical Interactions by Local Piezoelectric Effects

Piezoelectricity is a well‐established property of biological materials, yet its functional role has remained unclear. Here, a mechanical effect of piezoelectric domains resulting from collagen fibril organisation is demonstrated, and its role in tissue function and application to material design is described. Using a combination of scanning probe and nonlinear optical microscopy, a hierarchical structuring of piezoelectric domains in collagen‐rich tissues is observed, and their mechanical effects are explored in silico. Local electrostatic attraction and repulsion due to shear piezoelectricity in these domains modulate fibril interactions from the tens of nanometre (single fibril interactions) to the tens of micron (fibre interactions) level, analogous to modulated friction effects. The manipulation of domain size and organisation thus provides a capacity to tune energy storage, dissipation, stiffness, and damage resistance.     

Co/SiO2 catalysts prepared from Co2(CO)8 for CO hydrogenation into alcohols and hydrocarbons: characterization by magnetic methods and temperature-programmed hydrogenation

The hydrogenation of carbon monoxide over Co/SiO₂ catalysts obtained by reduction of precursors prepared by the reaction of dicobaltoctacarbonyl with silica gives rise to a mixture of alcohols and hydrocarbons. The chain growth probability for hydrocarbon synthesis is similar to that observed over conventional catalysts prepared by the ammonia method (=0.74) with a comparable metal dispersion (metal particle size 4 nm). Alcohol formation yields a smaller chain growth probability (=0.42). Magnetic measurements have shown that in the latter catalyst, small cobalt clusters (1 nm) are likely to be present together with the cobalt particles (4 nm), this observation reconciles apparently conflicting results from the literature. It has been speculated that alcohol formation might be related to the presence of these clusters according to a concerted mechanism. Furthermore, the observation of large amounts of acetates by temperature-programmed hydrogenation, not detected in hydrocarbon selective catalysts, suggests that they may play a role in ethanol synthesis.     

On the determination of Poisson’s ratio of stressed monolayer and bilayer submicron thick films

In this paper, the bulge test is used to determine the mechanical properties of very thin dielectric membranes. Commonly, this experimental method permits to determine the residual stress (σ₀) and biaxial Young’s modulus (E/(1 − υ)). Associating square and rectangular membranes with different length to width ratios, the Poisson’s ratio (υ) can also be determined. LPCVD Si₃N₄ monolayer and Si₃N₄/SiO₂ bilayer membranes, with thicknesses down to 100 nm, have been characterized giving results in agreement with literature for Si₃N₄, E = 212 ± 14 GPa, σ₀ = 420 ± 8 MPa and υ = 0.29.     

Thermal Resistance Minimization of a Fin-and-Porous-Medium Heat Sink with Evolutionary Algorithms

This article presents a conceptual design of a heat sink combining a porous medium whose matrix is highly conductive and a fin. A simplified model is presented to estimate the performance of the system, relying on Darcy law and local thermal equilibrium. The objective is to minimize the hot-spot temperature under global mass constraint by using an optimization procedure based on genetic algorithms. The design variables are the porosity and material of each layer of the porous medium, the fin material, height, and width, the aspect ratio of the heat sink, and the shape of a weightless upper corner deflector which reduces the width of the inlet and outlet air slots while removing the less useful mass. Results show that the optimal porous layers were generally of copper, independent of the mass constraint. However, the fin is mostly beneficial for heavier designs, while the deflector becomes more important when lightness is required. These two special features show their efficiency by allowing a mass reduction of 95% with a decrease of only 24% in the cooling performance.