Carbon Dioxide Reduction on Transition Metal Dichalcogenides with Ni and Cu Edge Doping: A Density-Functional Theory Study

Transition-metal dichalcogenides (TMDs) have promising properties for their use as catalysts of CO₂ reduction to methane via the Sabatier reaction. In this article we use density-functional theory calculations to gain insight into the energetics of this reaction for Mo/W-based and S/Se-based TMDs with non-, Ni- and Cu-doping. We show that sulfur-based TMDs with Ni/Cu doping exhibit better indicators for catalytic performance of the CO₂ reduction reaction than non-doped and doped TMDs without active sites. In addition, the role of the transition metal was found to a much smaller influence in the reaction than the role of the chalcogen and dopant atoms, which influence the bonding strength and type, respectively.     

Size and branching effects on the fluorescence of benzylic dendrimers possessing one apigenin fluorophore at the core

Different generations of dendrimers incorporating one fluorescent core of apigenin and three Fréchet benzylic dendrons have been prepared. The chief geometric features of these dendrimers have been obtained by Molecular Dynamics simulations. These computational data suggest that the asphericities of dendrimers belonging to the third and fourth generations are considerably larger than those associated with lower radii of gyration. Fluorescence spectra of high generation dendrimers evolve along time and quantum yields show an appreciable lowering for the fourth generation dendrimer. All these data suggest aggregation phenomena and lower quantum yields for nonspheric dendrimers in solution.     

The effect of negatively charged metallic nanocatalysts on their reactions with alkyl radicals

Abstract

Stored electrons on Au and Ag nanoparticles (NPs) have been found to catalyze various reduction processes initiated by ionizing irradiation or light illumination in which the NPs act as “nano-electrodes”. In the present study, we explored the effect of charging colloidal gold and silver NPs on their reaction with methyl radicals, ·CH₃. The results show that charging the colloidal metal NPs by excess of electrons, (NP)^n?, affected their reaction mechanism with methyl radicals and resulted in different product composition in comparison to the analogous reactions with uncharged particles. These results should be considered in photo(electro)catalytic processes when alkyl radicals are formed near the catalyst surface.     

Aggregation and Cooperative Effects in the Aldol Reactions of Lithium Enolates

Density functional theory and Car–Parrinello molecular dynamics simulations have been carried out for model aldol reactions involving aggregates of lithium enolates derived from acetaldehyde and acetone. Formaldehyde and acetone have been used as electrophiles. It is found that the geometries of the enolate aggregates are in general determined by the most favorable arrangements of the point charges within the respective Li_nO_n clusters. The reactivity of the enolates follows the sequence monomer?dimer>tetramer. In lithium aggregates, the initially formed aldol adducts must rearrange to form more stable structures in which the enolate and alkoxide oxygen atoms are within the respective Li_nO_n clusters. Positive cooperative effects, similar to allosteric effects found in several proteins, are found for the successive aldol reactions in aggregates. The corresponding transition structures show in general sofa geometries.     

The geometry of the asymptotics of polynomial maps

The aim of this paper is to develop a theory for the asymptotic behavior of polynomials and of polynomial maps overR and overC and to apply it to the Jacobian conjecture. This theory gives a unified frame for some results on polynomial maps that were not related before. A well known theorem of J. Hadamard gives a necessary and sufficient condition on a local diffeomorphismf: R ⁿ →R ⁿ to be a global diffeomorphism. In order to show thatf is a global diffeomorphism it suffices to exclude the existence of asymptotic values forf. The real Jacobian conjecture was shown to be false by S. Pinchuk. Our first application is to understand his construction within the general theory of asymptotic values of polynomial maps and prove that there is no such counterexample for the Jacobian conjecture overC. In a second application we reprove a theorem of Jeffrey Lang which gives an equivalent formulation of the Jacobian conjecture in terms of Newton polygons. This generalizes a result of Abhyankar. A third application is another equivalent formulation of the Jacobian conjecture in terms of finiteness of certain polynomial rings withinC[U, V]. The theory has a geometrical aspect: we define and develop the theory of etale exotic surfaces. The simplest such surface corresponds to Pinchuk's construction in the real case. In fact, we prove one more equivalent formulation of the Jacobian conjecture using etale exotic surfaces. We consider polynomial vector fields on etale exotic surfaces and explore their properties in relation to the Jacobian conjecture. In another application we give the structure of the real variety of the asymptotic values of a polynomial mapf: R ² →R ² .     

The Effect of Oil Price on the Optimal Speed of Ships

The tradeoff between fuel savings through slow steaming on the one hand, and the loss of revenues due to the resulting voyage extension on the other hand is analyzed, and three models for the explicit determination of the optimal speed of a ship are presented. Each model is applicable under different schedule of revenues, and the optimal speed is a solution to a cubic equation over the feasible range of cruising speeds.     

The development and influence of gas bubbles in phreatic aquifers under natural flow conditions

In a phreatic aquifer, bubbles may result from the entrapment of air during groundwater recharge and/or bacterial metabolism. The calculated critical depth of about 1 m at which bubbles are most likely to be found in a granular aquifer, coincides with the depth of 0.60 m of an almost stagnant water layer (specific discharge 1 × 10^-6 cm sec^-1) found at the water table region under natural flow conditions. Bubbles clog pores and therefore reduce the hydraulic conductivity without significantly reducing the volumetric water content. Stagnation at the water table region results since prevailing pressures (in the order of 10^-1 atmospheres) are not sufficiently large to move bubbles through porous media in a water environment.