Molecular Dynamics Study on the Demulsification Mechanism of Water-In-Oil Emulsion with SDS Surfactant under a DC Electric Field.

Application of an electric field is an effective demulsification method for water-in-oil (W/O) emulsions. For the W/O emulsions stabilized by anionic surfactants, the microscopic demulsification mechanism is still not very clear. In this work, the coalescence behavior of two droplets stabilized by the anionic surfactant sodium dodecyl sulfate (SDS) in the oil phase under a DC electric field is investigated by molecular dynamics simulation. The effects of electric field strength and oil type on the electrocoalescence of two water droplets are mainly considered. The trajectory snapshots and center of mass of the two water droplets suggest that there is almost no migratory coalescence. The movement of sodium ions and SDS, which is a combined effect of the electric field force and the resistance from the oil phase, is crucial for the deformation and connection of two water droplets. The results of mean square displacement, radial distribution function, hydration number, and interaction energies of Na+-H2O and SDS-H2O indicate that the sodium ion has a stronger ability to carry water molecules for movement than SDS. The stronger electric field strength will result in more severe deformation and shorter coalescence time. Under the higher electric field strength, the two droplets will be elongated into a slender water ribbon. By applying a pulsed DC electric field with suitable amplitude, frequency, and duty ratio, it is possible to achieve full coalescence for the ionic surfactant-stabilized W/O emulsions. The oil phase also plays an important role for the deformation of droplets and the migration of emulsion components. For the different oil phases, a longer time or stronger electric field strength would be needed for the electrocoalescence of droplets in the oil phase with higher density and viscosity. Our results are expected to be helpful for practical application in the petroleum industry and chemical engineering.

A mechanism study of sodium dodecylbenzene sulfonate on oil recovery: effect of branched chain structure.

The effects of the branched structures of SDBS molecules on oil recovery are investigated by molecular dynamics method. The relative density of oil molecules shows that SDBS molecule with benzene ring located near the center of alkyl chain has the best effect on oil displacement. Dynamic trajectories show that the water and SDBS molecules gradually occupy the calcite surface and replace the oil droplets. In this process, more water molecules gather nearby the polar groups of SDBS, indicating that the polar group has a significant effect on the water infiltration and the formation of water channels. Contact angle between SDBS molecule and calcite surface indicates that compared to straight chains, the branched structure tends to spread on the calcite interface. Moreover, adsorption energies of the simulation systems further prove that as the aromatic ring is closer to the middle of the alkyl chain, the oil displacement effect is better.

Effect of electric field on coalescence of an oil-in-water emulsion stabilized by surfactant: a molecular dynamics study.

The microscopic understanding of electrocoalescence of oil-in-water (O/W) emulsions stabilized by surfactant is very important to improve the efficiency of electrical demulsification. The behaviors of the coalescence of O/W emulsion stabilized by surfactant in the presence of a direct electric field and a pulsed electric field were explored by nonequilibrium molecular dynamics simulations. According to the simulated results, an electrical method is feasible to demulsify an O/W emulsion stabilized by a surfactant. The configuration and movement of the sodium dodecyl sulfate (SDS) were determined by interactions between SDS molecules themselves and between SDS and oil/water molecules along with the force exerted by the applied electrical field. Two droplets will coalesce into one when the strength of the electric field exceeds 0.4 V nm-1. The SDS group can be broken up by an electric field larger than 0.6 V nm-1. The point when interaction energy between the hexadecane molecules of the two droplets begins to decrease from zero is consistent with the time when the two oil droplets came in contact. The coalescence process can be completed if the two droplets have begun to coalesce, even after the electric field was removed. Otherwise, the coalescence process cannot be completed. To enhance the efficiency of the electrocoalescence of O/W emulsions, strength, frequency and duty ratio of the electric field have to be optimized according to the properties of the emulsion. This research will help us to figure out how electric fields promote the efficiency of electrocoalescence of O/W emulsions with surfactant.

Theoretical studies of electron transport in thiophene dimer: effects of substituent group and heteroatom.

The electron-transport properties of various substituted molecules based on the thiol-ended thiophene dimer (2Th1DT) are investigated through density functional theory (DFT) combined with nonequilibrium Green's function (NEGF) method. The current-voltage (I-V) curves of all the Au/2Th1DT/Au systems in this work display similar steplike features, while their equilibrium conductances show a large difference and some of these I-V curves are asymmetric distinctly. The results reveal the dependence of conductance on the energy level of the substituted 2Th1DT molecules. Rectification ratios are computed to examine the asymmetric properties of the I-V curves. The rectifying behavior in the 2Th1DT molecule containing the amino group close to the molecular end is more prominent than that in the other molecules. The rectifying behavior is analyzed through transmission spectra and molecular projected self-consistent Hamiltonian (MPSH) states. Slight negative differential resistance (NDR) can be observed in some of the systems. The electron-transport properties of 2Th1DT molecules containing different heteroatoms are also investigated. The results indicate that the current in heteroatom-containing molecules is larger than that in their pristine analogues, and lighter heteroatoms are more favorable than heavier heteroatoms for electron transport of the thiophene dimer.

First-principles study of rectification in bis-2-(5-ethynylthienyl)ethyne molecular junctions.

Using density functional theory (DFT) combined with the first-principles nonequilibrium Green's function (NEGF), we investigated the electron-transport properties and rectifying behaviors of several molecular junctions based on the bis-2-(5-ethynylthienyl)ethyne (BETE) molecule. To examine the roles of different rectification factors, asymmetric electrode-molecule contacts and donor-acceptor substituent groups were introduced into the BETE-based molecular junction. The asymmetric current-voltage characteristics were obtained for the molecular junctions containing asymmetric contacts and donor-acceptor groups. In our models, the computed rectification ratios show that the mode of electrode-molecule contacts plays a crucial role in rectification and that the rectifying effect is not enhanced significantly by introducing the additional donor-acceptor components for the molecular rectifier with asymmetric electrode-molecule contacts. The current-voltage characteristics and rectifying behaviors are discussed in terms of transmission spectra, molecular projected self-consistent Hamiltonian (MPSH) states, and energy levels of MPSH states.

Effect of the linkage modes of thiolated ethynyl groups on the spin-dependent electronic transport properties in transition metal porphyrin molecular junctions.

Using density functional theory and nonequilibrium Green's function method, the spin-dependent electronic transport properties of six transition metal porphyrin molecules (VP, CrP, MnP, FeP, CoP, and NiP), which are linked to gold electrodes through the thiolated ethynyl groups, are investigated. Two different linkage modes (beta linkage and meso linkage) of the substituted ethynyl groups on the porphyrin macrocycle are considered. The results show that the linkage mode of ethynyl groups plays an important role on the spin transport properties of the molecular junctions and the beta linkage is more favorable for the spin filtering efficiency of current than the meso linkages. The spin-up and spin-down energy levels show the different evolutions which is responsible for the difference of spin filtering efficiency between the two linkage modes. The computational results of total current show that the meso-linked molecular junctions have the better conductive performances than the beta-linked ones which may be caused by the different electronic transport paths.

Theoretical study of T shaped phenothiazine/carbazole based organic dyes with naphthalimide as π-spacer for DSSCs.

Eight novel T shaped phenothiazine/carbazole based organic dyes with naphthalimide as π-spacer were designed, and the geometries, electronic structures, and optical features of these isolated dyes and dye-(TiO2)9 systems were investigated with density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations. Some quantify factors influencing the energy conversion efficiency (PCE) such as the light harvesting efficiency (LHE), electron injection driving force (ΔGinject) and dye regeneration driving force (ΔGreg) were also calculated for dye-sensitized solar cells (DSSCs) applications. It is found that these dyes show a good performance of electron injection and dye regeneration owing to the proper value of ΔGinject and ΔGreg. The optimized geometries of the non-planar molecular configuration of donor and the planar structure of the naphthalimide conjugated bridge are beneficial to efficient intramolecular charge transfer and the suppression of molecular aggregation. The properties about the electronic structure and absorption spectra indicate that replacement of benzene with thiophene unit near to cyanoacetic acid acceptor can generate more efficient conjugation effect and achieve red shift of absorption spectra, resulting a higher Jsc and Voc in DSSCs device. The theoretical results reveal that DTPH2, DTPH4, DTCA2 and DTCA4 would be used as potential sensitizers for DSSCs applications.

DFT/TD-DFT study of novel T shaped phenothiazine-based organic dyes for dye-sensitized solar cells applications.

Five novel T shaped phenothiazine-based organic dyes DTTP1~5 with different spacers at N (10) position were designed. The geometries, electronic structures, absorption spectra, electron transfer and injection properties of these isolated dyes and dye/(TiO2)9 systems were investigated via density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculation. The optimized geometries indicate that these T shaped dyes show non-planar conformations, which are helpful in suppressing the close intermolecular π-π aggregation in device and enhancing thermal stability. The calculated results indicate that type of π-conjugated spacers can affect the molecular absorption spectra. Introduction of thiophene-benzothiadizole-thiophene unit as π-conjugated spacer can most effectively shift the light absorption to near infrared region and enhance the light harvesting efficiency (LHE). Moreover, it is found that these dyes show a good performance of electron injection and dye regeneration owing to the proper electron injection driving force (ΔGinject) and dye regeneration driving force (ΔGreg). The theoretical results reveal that these dyes could be used as potential sensitizers for DSSCs, and DTTP4 would be the most plausible sensitizer for high-efficiency DSSCs due to the narrow HOMO-LUMO energy gap (ΔH-L), broad absorption spectrum, high LHE value, and large dipole moment (µnormal).

Theoretical Studies of the Spin-Dependent Electronic Transport Properties in Ethynyl-Terminated Ferrocene Molecular Junctions.

The spin-dependent electron transport in the ferrocene-based molecular junctions, in which the molecules are 1,3-substituted and 1,3'-substituted ethynyl ferrocenes, respectively, is studied by the theoretical simulation with nonequilibrium Green's function and density functional theory. The calculated results suggest that the substitution position of the terminal ethynyl groups has a great effect on the spin-dependent current-voltage properties and the spin filtering efficiency of the molecular junctions. At the lower bias, high spin filtering efficiency is found in 1,3'-substituted ethynyl ferrocene junction, which suggests that the spin filtering efficiency is also dependent on the bias voltage. The different spin-dependent transport properties for the two molecular junctions originate from their different evolutions of spin-up and spin-down energy levels.