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In dimethyl sulfoxide electrolytes, the existence of water can lead to changes occurring in the zinc-ionintercalated phase. A Zn-birnessite, when replaced by a super-hydrated Zn-buserite, enhanced solid-phase diffusion and surface kinetics.

This study aims to synthesize α,β-unsaturated carbonyl compounds with branched structures via aldol condensation of furfural and 2-butanone using magnesium–aluminum (MgAl) mixed oxides as heterogeneous acid–base catalysts. Regarding the molecular structure of 2-butanone, there are two possible enolate ions generated by subtracting the α-hydrogen atoms at the methyl or methylene groups of 2-butanone. The branched-chain C9 products, derived from the methylene enolate ion, can be applied as bio-jet fuel precursors. The most suitable catalyst, contributing the highest furfural conversion (63%) and selectivity of the branched-chain C9 products (77%), is LDO3, the mixed oxides with 3:1 Mg:Al atomic ratio, with a high surface area and a large number of medium basic sites. The suitable reaction conditions to produce the branched-chain C9 ketones are 1:5 furfural:2-butanone molar ratio, 5 wt.% catalyst loading, 120 °C reaction temperature, and 8 h reaction time. Additionally, this study investigates the adsorption of 2-butanone onto a mixed oxide using in situ Fourier transform infrared spectroscopy; the results of which suggest that the methylene enolate of 2-butanone is the likely dominant surface intermediate at elevated temperatures. Accordingly, the calculation, based on density functional theory, indicates that the methylene enolate ion of 2-butanone is the kinetically favorable intermediate on an MgO(100) as a model oxide surface.

In our previous simulation study [J. Phys. Chem. C, 2011, 115, 17286], branched sodium dodecyl benzene-sulfonate (SDBS) surfactants showed self-assembled structures on single-walled carbon nanotubes (SWNTs) that were strongly dependent on tube diameter. Those results suggested that branched SDBS, as opposed to their linear counterparts, could specifically stabilize SWNTs of narrow diameter. Experimental data, however, show that SDBS stabilizes aqueous SWNTs of many diameters. This discrepancy between simulated and experimental results could be explained by the fact that experimental SDBS samples are isomeric mixtures. To test this possibility we report here molecular dynamics (MD) simulation results for equimolar mixtures of aqueous linear and branched SDBS on (6,6) and (20,20) SWNTs at ambient conditions. Our results suggest that there is no strong effect due to nanotube diameter on the morphology of mixed SDBS surfactant aggregates, although the adsorbed aggregate structure strongly depends on surfactant coverage. In-plane radial distribution functions suggest that linear and branched molecules distribute evenly onto the surfaces of (6,6) SWNTs, while some evidence of segregation, in which branched SDBS predominantly pack near other branched molecules, was obtained on (20,20) SWNTs at high surface coverage. These results suggest that the lack of specificity in stabilizing aqueous dispersions of carbon nanotubes using SDBS surfactants is probably due to the presence of multiple isomeric molecules in commercial surfactant samples. Perhaps more importantly, these simulations suggest that using mixtures of surfactants could affect the structure of the adsorbed aggregates, and the stability of aqueous dispersion of carbon nanotubes.

Using coarse-grained dissipative particle dynamics (DPD) simulations, we systematically study the effect of surface heterogeneity on surfactant adsorption. Here we investigate the adsorption and aggregation of surfactants on hydrophobic stripes crossing each other perpendicularly (i.e., crossing stripes) and on hydrophobic steps. The results are compared with those obtained for isolated stripes. We find that on crossing stripes of moderate stripe widths (e.g., L = 0.61LS, 1.22LS and 1.83LS, where LS is the length of one surfactant molecule) the crossing region hinders the formation of defect-free adsorbed surfactant structures. By increasing the stripe width and/or by increasing the length of one of the two perpendicularly crossing stripes (i.e., lowering the surface density of defects/intersections), the crossing region is found to have a weaker effect on the features of the adsorbed structures. Regarding surfactant adsorption on steps, our simulation results show that the self-assembled aggregates can be stretched along the step corner, and the resultant elastic deformation can hinder adsorption. This qualitative observation can facilitate a description of surfactant adsorption that takes into consideration also the deformation of the self-assembled film. As suggested by such a general model, increasing the convex angle of the step, increasing the size of the surfactant head groups, and changing other physical parameters can reduce the elastic energy penalty, and yield larger amounts of surfactants adsorbed. The results presented could assist in understanding and sometimes predicting surfactant adsorption on heterogeneous surfaces, suggest methods to formulate surfactant mixtures to control surface coverage on heterogeneous surfaces, and perhaps facilitate new methods for the fabrication of nano-structured surfaces.

Stabilizing single-walled carbon nanotubes (SWNTs) monodispersed in diameter and chirality in aqueous media remains elusive. Surfactants have proven useful in deploying ultracentrifugation techniques for separating carbon nanotubes, but the molecular mechanism responsible for the effectiveness for such technique remains not fully understood. On the basis of recent molecular simulation results, it appears that the morphology of self-assembled surfactant aggregates on carbon nanotubes strongly affects the effective potential of mean force between pairs of interacting carbon nanotubes. In the present work, the effect of surfactant molecular structure on the properties of aqueous surfactant self-assembled aggregates was investigated using all-atom molecular dynamics simulations. To quantify how the surfactant molecular structure affects self-assembly, sodium dodecylbenzenesulfonate (SDBS) surfactants with the headgroup located either on the fifth or on the twelfth carbon atom along the dodecyl tail were consi...

Self-assembly is widely seen as the method of choice for the bottom-up manufacture of supra-colloidal aggregates. Surfactants have been used extensively to appreciate qualitatively and quantify driving forces and methodologies for controlling self-assembling processes and the resultant self-assembled aggregates. However, not much is known regarding self-assembled surfactant aggregates formed on heterogeneous surfaces. If heterogeneous surface features affect the morphology of surfactant aggregates, it is possible that new templating methodologies could be designed by engineering surfaces. Here we report equilibrium dissipative particle dynamics simulation results for surfactants adsorbed on model heterogeneous surfaces. Our simulation results reveal that, depending on the morphological and chemical properties of the solid substrate, a number of not-before-reported structures can be obtained for the self-assembled aggregates. The results presented could be useful for the manufacture of new coatings and materials, e.g., via the admicellar polymerization procedure, as well as for interpreting experimental data for surfactant adsorption on heterogeneous surfaces.

The adsorption and self-assembly of surfactants are ubiquitous processes in several technological applications, including the manufacture of nano-structured materials using bottom-up strategies. Although much is known about the adsorption of surfactants on homogeneous flat surfaces from experiments, theory, and simulations, limited information is available, in quantifiable terms, regarding the adsorption of surfactants on surfaces with chemical and/or morphological heterogeneity. In an effort to fill this knowledge gap, we report here results obtained using equilibrium dissipative particle dynamics (DPD) simulations for the adsorption of model surfactants onto patterned flat surfaces (i.e., flat surfaces with chemical heterogeneity). The patterns consist of one or two stripes of variable width on which the surfactants could adsorb. The adsorbing stripes are surrounded by a surface that effectively repels the surfactants. This repelling surface, perhaps not realistic, allows us to quantify the effect of lateral confinement on the morphology of surfactant aggregates. When the stripe width is large (effectively providing a homogeneous flat surface), the surfactants yield a flat monolayer. Our simulations suggest that the flat monolayers become hemi-cylinders, hemi-spheres, and individual surfactants as the stripe width decreases, a consequence of lateral confinement. In some cases our simulations show evidence of cooperative effects when two adsorbing stripes are present on the surface. If the distance between the stripes and the widths of the stripes are both less than about one surfactant length, hemi-cylindrical shells and irregular structures are observed because of cooperativity; otherwise the results match those found for a single isolated stripe. Our predictions could be useful for the design of new nano-structured materials and coatings, for applications ranging from nano-fluidic devices to nano-reactors.

Tremendous progress has been made to stabilize carbon nanotube dispersions using surfactants, although many questions await answer to design surfactant formulations that selectively stabilize nanotubes mono-dispersed in diameter and chirality. Stimulated by recent experimental observations [J. Am. Chem. Soc., 2010, 132, 16165–16175], we attempt here to quantify how changing the counter-ion (Cs+ instead of Na+) affects the morphology of dodecyl sulfate surfactants adsorbed on carbon nanotubes. Using atomistic molecular dynamics we simulated aqueous cesium dodecyl sulfate (CsDS) adsorbed on (6,6), (12,12), and (20,20) single-walled carbon nanotubes (SWCNTs) at ambient conditions. When compared to results for sodium dodecyl sulfate (SDS), our results suggest that surface aggregates with Cs+ ions, compared to Na+, yield a more compact coverage of the nanotubes at the surfactant surface coverage of 0.25 nm2 per headgroup, with the surfactant heads extended towards the bulk aqueous solution, and prevent water from accessing the nanotube surface. These morphological results suggest that CsDS should be more effective than SDS at stabilizing aqueous carbon nanotubes dispersions. More importantly, these results were obtained only for the (6,6) nanotubes simulated. For the wider nanotubes our simulations show limited, if any, differences in the morphology of the surfactant aggregates when the Na+ ions are substituted with Cs+ ones. To validate our results we measured experimental UV-Vis-NIR absorbance spectra for aqueous carbon nanotubes with diameters similar to that of (6,6) and of (12,12) nanotubes stabilized by SDS at increasing salt concentration (CsCl vs. NaCl). The results are indicative of changes in the surfactant self-assembled structure on the narrow nanotubes in the presence of Cs+ ions, while data for the wider tubes only suggest salt-screening effects for both Na+ and Cs+ ions. The different salt-specific behavior observed for the surfactants adsorbed on narrow vs. wide carbon nanotubes could be exploited for the selective stabilization of mono-dispersed carbon nanotube samples, although a surfactant more effective than SDS should be used.