Jingcun Fan

Microstructural heterogeneities arising from molecular clusters directly affect the nonlinear thermodynamic properties of supercritical fluids. We present a physical model to elucidate the relation between energy exchange and heterogeneous cluster dynamics during the transition from liquidlike to gaslike conditions. By analyzing molecular-dynamics data and employing physical principles, the model considers contributions from three key processes, namely, changing cluster density, cluster separation, and transfer of molecules between clusters. We show that the proposed model is consistent with the energetics at subcritical conditions and can be used to explain the nonlinear behavior of thermodynamic response functions, including the peak in the isobaric heat capacity.

Supercritical mixtures of ethanol (EtOH) and carbon dioxide (CO2) are classified as type-I mixtures, with complete macroscopic miscibility. However, differences in molecular polarity and interactions suggest a distinct phase behavior at the microscopic level. Here, we combine Small Angle X-ray Scattering experiments and molecular dynamics (MD) simulations to investigate the microscopic structure of EtOH–CO2 mixtures under supercritical conditions. The structure factor exhibits non-linear composition-dependent behavior, revealing pronounced local density fluctuations. The complementary MD simulations, using optimized force field parameters, provide atomistic insight, showing that EtOH forms self-associated, hydrogen-bonded aggregates, while CO2 remains more uniformly distributed. Cluster analysis identifies a preferential EtOH-rich composition exceeding the bulk average, governed by a balance between energetic and entropic competition. These results demonstrate that, contrary to macroscopic expectations, the mixture exhibits significant microscopic heterogeneity and immiscibility, which may influence solubility, reactivity, transport properties, and thermodynamic response functions. These findings challenge the conventional views of type-I fluids and emphasize the necessity of revising mixture states and considering molecular polarity.

Desalination can help to alleviate the fresh-water crisis facing the world. Thermally driven membrane distillation is a promising way to purify water from a variety of saline and polluted sources by utilizing low-grade heat. However, membrane distillation membranes suffer from limited permeance and wetting owing to the lack of precise structural control. Here, we report a strategy to fabricate membrane distillation membranes composed of vertically aligned channels with a hydrophilicity gradient by engineering defects in covalent organic framework films by the removal of imine bonds. Such functional variation in individual channels enables a selective water transport pathway and a precise liquid–vapour phase change interface. In addition to having anti-fouling and anti-wetting capability, the covalent organic framework membrane on a supporting layer shows a flux of 600 l m–2 h–1 with 85 °C feed at 16 kPa absolute pressure, which is nearly triple that of the state-of-the-art membrane distillation membrane for desalination. Our results may promote the development of gradient membranes for molecular sieving.

We investigate the underlying mechanism of capillary force balance at the contact line. In particular, we offer a novel approach to describe and quantify the capillary force on the liquid in coexistence with its vapor phase, which is crucial in wetting and spreading dynamics. Its relation with the interface tension is elucidated. The proposed model is verified by our molecular dynamics simulations over a wide contact angle range. Differences in capillary forces are observed in evaporating droplets on homogeneous and decorated surfaces. Our findings not only provide a theoretical insight into capillary forces at the contact line, but also validate Young’s equation based on a mechanical interpretation.

We investigate the capillary force balance at the contact line on rough solid surfaces and in two-liquid systems. Our results confirm that solid-liquid interactions perpendicular to the interface have a significant influence on the lateral component of the capillary force exerted on the contact line. Surface roughness of the solid substrate reduces the mobility of liquid and alters how the perpendicular solid-liquid interactions transfer into a force acting parallel to the interface. A quantitative relation between surface roughness and the transfer strategy is proposed. Moreover, when a liquid is in coexistence with another immiscible liquid on a solid, the capillary forces exerted on liquids of both sides are involved in our theoretical model. The contact angle can be predicted by calculating three interfacial tensions. These arguments are then verified by molecular dynamics simulations. Our findings set up the generalized theoretical framework for the capillary force balance at the contact line and broaden its application in more realistic scenarios.

Evaporation-driven liquid flow through nanochannels has attracted extensive attention over recent years due to its applications in mass and heat transfer as well as energy harvesting. A more comprehensive understanding is still expected to reveal the underlying mechanisms and quantitatively elucidate the transport characteristics of this phenomenon. In this study, we investigated evaporation-driven liquid flow through nanochannels using molecular dynamics simulations. The evaporation flux from the solid-liquid interface was higher than that from the middle region of the channel or the liquid-vapor interface. This finding may explain why experimental observations of evaporation flux through nanochannels exceed the limits predicted by the classical Hertz–Knudsen equation. Upon increasing the interaction strength between liquid atoms, the liquid exhibited enhanced solid-liquid interfacial evaporation and higher surface tension, albeit with reduced total flux. We also found that lyophilic channels exhibited higher evaporation fluxes than lyophobic channels, which can be interpreted by a Gibbs free energy analysis. The energy conversion analysis indicated that the effective pressure gradient exerted on a liquid flow by evaporation depends on the channel length. This was consistent with our simulations. Evaporation-driven liquid flow through nanochannels could be modeled quantitatively using this knowledge.

Polymer flooding is a promising chemical enhanced oil recovery (EOR) method, which realizes more efficient extraction in porous formations characterized with nanoscale porosity and complicated interfaces. Understanding the molecular mechanism of viscoelastic polymer EOR in nanopores is of great significance for the advancement of oil exploitation. Using molecular dynamics simulations, we investigated the detailed process of a viscoelastic polymer displacing oil at the atomic scale. We found that the interactions between polymer chains and oil provide an additional pulling effect on extracting the residual oil trapped in dead-end nanopores, which plays a key role in increasing the oil displacement efficiency. Our results also demonstrate that the oil displacement ability of polymer can be reinforced with the increasing chain length and viscoelasticity. In particular, a polymer with longer chain length exhibits stronger elastic property, which enhances the foregoing pulling effect. These findings can help to enrich our understanding on the molecular mechanism of polymer enhanced oil recovery and provide guidance for oil extraction engineering.