Ultrafast nanoporous silica formation driven by femtosecond laser irradiation

A type of glass modifications occurring after femto‐second laser irradiation gives rise to strong (10⁻²) from birefringence. This form birefringence is thought to be related to index nanostructure (called nanogratings). Analyzing induced tracks in fused silica using scanning electron microscopy (SEM) with nm resolution shows that nanostructures are porous nanoplanes with an average index lower than typical silica (Δn ∼ –0.20). Their origin is explained as arising from fast decomposition of the glass under localized, high‐intensity femtosecond laser radiation where strong nonlinear, multiphoton‐induced photoionization leads to plasma generation. Mechanistic details include Coulombic explosions characteristic of strong photoionization and the production of self‐trapped exciton (STE). Rapid relaxation of these STE prevents recombination and dissociated atomic oxygen instead recombines with each other to form molecular oxygen pointed out using Raman microscopy. Some of it is dissolved in the condensed glass whilst the rest is trapped within nanovoids. A chemical recombination can only occur at 1200 °C for many hours. This explains the thermal stability of such a nanostructure. Precise laser translation and control of these birefringent nanoporous structures allo arbitrarily tuning and positioning within the glass, an important tool for controlling optical properties for photonic applications, catalysts, molecular sieves, composites and more.     

Local Regularity for Parabolic Nonlocal Operators

Weak solutions to parabolic integro-differential operators of order α ∈ (α₀, 2) are studied. Local a priori estimates of Hölder norms and a weak Harnack inequality are proved. These results are robust with respect to α↗2. In this sense, the presentation is an extension of Moser's result from [20 Moser , J. ( 1971 ). On a pointwise estimate for parabolic differential equations . Comm. Pure Appl. Math. 24 : 727 – 740 .[Crossref], [Web of Science ®] , [Google Scholar]].     

Aqueous Electrochemical Reduction of Carbon Dioxide and Carbon Monoxide into Methanol with Cobalt Phthalocyanine

Conversion of CO₂ into valuable molecules is a field of intensive investigation with the aim of developing scalable technologies for making fuels using renewable energy sources. While electrochemical reduction into CO and formate are approaching industrial maturity, a current challenge is obtaining more reduced products like methanol. However, literature on the matter is scarce, and even more for the use of molecular catalysts. Here, we demonstrate that cobalt phthalocyanine, a well‐known catalyst for the electrochemical conversion of CO₂ to CO, can also catalyze the reaction from CO₂ or CO to methanol in aqueous electrolytes at ambient conditions of temperature and pressure. The studies identify formaldehyde as a key intermediate and an unexpected pH effect on selectivity. This paves the way for establishing a sequential process where CO₂ is first converted to CO which is subsequently used as a reactant to produce methanol. Under ideal conditions, the reaction shows a global Faradaic efficiency of 19.5 % and chemical selectivity of 7.5 %.     

On the Capability of the Generalized Gamma Function to Represent Spray Drop‐Size Distribution

The three‐parameter, Generalized Gamma function solution of a recent MEF formulation used to derive liquid spray drop‐size distribution, is applied to sprays resulting from three different atomization processes. The objectives of these applications are to determine the sign of the parameters for which this function reports a more reliable fit and to further understand the parameter stability problem reported elsewhere. It is found that the lack of stability of the parameters is related to a characteristic feature of the mathematical function and appears for a series of spray drop‐size distributions with constant shape. For each situation analyzed in the present study, the Generalized Gamma function provides a very good fit with parameters that are either constant or correlated to the working conditions. As far as the sign of the parameters is concerned, the results show that the best formulation is a function of the spray and that it is impossible to know, a priori, which parameter sign will report the best fit. Finally, for one situation, it is found that the Generalized Gamma function allows extrapolation of drop sizes outside the measured values. All of the results converge to conclude that the three‐parameter Generalized Gamma function, which is identical to the well‐known Nukiyama‐Tanasawa distribution, accumulates valuable attributes to represent liquid spray drop‐size distributions.     

“(Diphosphine)Nickel”‐Catalyzed Negishi Cross‐Coupling: An Experimental and Theoretical Study

The use of a strongly donating “(bis‐dialkylphosphine)Ni” fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni⁰/Ni^II cycle is operative in this system.     

Comparative Study of Alkali-Cation-Based (Li+, Na+, K+) Electrolytes in Acetonitrile and Alkylcarbonates

The development of a suitable functional electrolyte is urgently required for fast-charging and high-voltage alkali-ion (Li, Na, K) batteries as well as next-generation hybrids supercapacitors. Many recent works focused on an optimal selection of electrolytes for alkali-ion based systems and their electrochemical performance but the understanding of the fundamental aspect that explains their different behaviour is rare. Herein, we report a comparative study of transport properties for LiPF₆, NaPF₆, KPF₆ in acetonitrile (AN) and a binary mixture of ethylene carbonate (EC), dimethyl carbonate (DMC): (EC/DMC : 1/1, weigh) through conductivities, densities and viscosities measurements in wide temperature domain. By application of the Stokes-Einstein, Nernst-Einstein, and Jones Dole equations, the effective ionic solvated radius of cation (r_eff), the ionic dissociation coefficient (α_D) and structuring Jones Dole's parameters (A, B) for salt are calculated and discussed according to solvent or cation nature as a function of temperature. From the results, we demonstrate that better mobility of potassium can be explained by the nature of the ion-ion and ion-solvent interactions due to its polarizability. In the same time, the predominance of triple ions in the case of K⁺, is a disadvantage at high concentration.     

Direct C−H Carbamoylation of Nitrogen-Containing Heterocycles

Nucleophilic radical additions at innately electrophilic C(sp²) centers are perfectly suited for the direct functionalization of heterocycles. Using bench stable and commercially available alkyl oxamate and oxamic acid derivatives in combination with photoredox catalysis, a direct carbamoylation of heterocycles yielding amide functionalized pharmacophores in a single step is reported. The reaction conditions reported are compatible with structurally complex heterocyclic substrates of pharmaceutical interest. Notably, derivatives containing functional groups incompatible with standard amidation reactions, such as carboxylic acids and unprotected amines, were found to be amenable to this reaction paradigm.     

Metric Subregularity in Generalized Equations

In this article, we study the metric subregularity of generalized equations using a new tool of nonsmooth analysis. We obtain a sufficient condition for a generalized equation to be metrically subregular, which is not a necessary condition for metric regularity, using a subtle adjustment of the Mordukhovich coderivative. We apply these results to the study of the metric subregularity in a Cournot duopoly game.