Passive fractionating mechanism for oil spill using shear-wettability modulation.

Oil spillage and organic solvent leakage have been a frequent occurrence in recent years, which pose a significant threat not only to the aquatic ecosystems but also result in substantial economic burdens. This has necessitated the search for materials capable of separating oil from water at enhanced efficiency with superior mechanical and thermal properties. In this study, we conduct a set of systematic molecular dynamics simulations to investigate the potential of two-dimensional graphene-like channels under extreme confinement to achieve efficient oil-water separation. Effective modulation of the wetting characteristics of graphene-like surfaces juxtaposed with unconventional flow behavior at the nanoscale unveils differential interaction of water and oil molecules towards the wall, thereby resulting in distinct separation zones for varying compositions of the oil-water mixture. Such separation zones have been observed to be highly correlated with mixture temperature, which provides effective separation pathways across diverse environmental conditions. Our study offers a paradigm shift in oil-water separation strategies, which not only provides deeper insights into the equilibrium and dynamic behavior of a two-phase mixture but also holds immense implications for the development of smart, wettability-based oil separation devices.

Wettability-modulated behavior of polymers under varying degrees of nano-confinement.

Extreme confinement in nanochannels results in unconventional equilibrium and flow behavior of polymers. The underlying flow physics dictating such paradigms remains far from being understood and more so if the confining substrate is composed of two-dimensional materials, such as graphene. In this study, we conducted systematic molecular dynamics simulations to explore the effect of wettability, confinement, and chain length on polymer flow through graphene-like nanochannels. Altering the wetting properties of these membranes that structurally represent graphene results in substantial changes in the behavior of polymers of disparate chain lengths. Longer hydrocarbon chains (n-dodecane) exhibit negligible wettability-dependent structuring in narrower nanochannels compared to shorter chains (n-hexane) culminating in higher average velocities and interfacial slippage of n-dodecane under less wettable conditions. We demonstrate that the wettability compensation comes from chain entanglement attributed to entropic factors. This study reveals a delicate balance between wettability-dependent enthalpy and chain-length-dependent entropy, resulting in a unique nanoscale flow paradigm, thus not only having far-reaching implications in the superior discernment of polymeric flow in sub-micrometer regimes but also potentially revolutionizing various applications in the oil industry, including innovative oil transport, oil extraction, ion transport polymers, and separation membranes.

Coupling solute interactions with functionalized graphene membranes: towards facile membrane-level engineering.

Optimizing ion transport through nanoporous graphene membranes with intricate engineering at nanoscale levels finds applications ranging from ion segregation to desalination. Such membrane-level engineering often requires futuristic and state-of-the-art micro- and nanofabrication infrastructure making it less accessible to widespread applications. In this study, the effective membrane pore size is modulated using macroscopic membrane functionalization, which, when combined with the solute concentration, can prove to be facile nanoscale engineering towards achieving selectivity. By performing robust molecular dynamics (MD) simulations of aqueous NaCl solution through a nanoporous graphene membrane, we demonstrate that varying membrane wettability influences the structural organization of ions and water molecules both in the vicinity and inside the nanopore, which is manifested in the form of altered permeation characteristics. Moreover, the disparate solvation characteristics of the ionic species in conjunction with the variable van der Waals interactive forces affect the ion-selective nature (Cl- over Na+) of the membrane. The relative hydrophilization, resulting from the effective functionalization of the nanoporous graphene membrane, not only allows greater control over the permeation characteristics of ions and water molecules mediated by an altered depletion ratio but also gives rise to the ion-selective nature of the membrane, thus providing a sound understanding of the transport properties of ion-water solutions through nanoporous materials.

Upstream events dictate interfacial slip in geometrically converging nanopores.

Continuum computations of fluid flow in conduits approaching molecular scales are often executed with a certain level of abstractions via the imposition of a pre-defined slip condition at the wall. However, in reality, the interfacial slip may not be affixed a priori as a direct one-to-one mapping with the surface wettability and charge but is implicitly interconnected with the concomitant dynamical events that may be effectively captured only under flow conditions. The flow in nanofluidic channels with axially varying cross sections hallmarks such situations in which the effective slip at the wall gets dynamically modulated by upstream flow conditions and cannot be trivially stamped as guided by localized intermolecular interactions over interfacial scales alone. In an effort to capture such flows without resorting to full-domain molecular dynamics simulations, here we bring out advancements on hybrid molecular-continuum simulations and report predictions that closely capture molecular dynamics based predictions of water transport through converging nanopores. Our results turn out to be of significant implications toward designing of emerging nanoscale devices of multifarious applications ranging from miniaturized reactors to highly targeted drug delivery systems.