Resolving Temperature-Dependent Hydrate Nucleation Pathway: The Role of "Transition Layer".

Understanding the nucleation of natural gas hydrate (NGH) at different conditions has important implications to NGH recovery and other industrial applications, such as gas storage and separation. Herein, vast numbers of hydrate nucleation events are traced via molecular dynamics (MD) simulations at different degrees of supercooling (or driving forces). Specifically, to precisely characterize a hydrate nucleus from an aqueous system during the MD simulation, we develop an evolutionary order parameter (OP) to recognize the nucleus size and shape. Subsequently, the free energy landscapes of hydrate during nucleation are explored by using the newly developed OP. The results suggest that at 270 K (or 0.92 Tm supercooling, where Tm is the melting point), the near-rounded nucleus prevails during the nucleation, as described from the classical nucleation theory. In contrast, at relatively strong driving forces of 0.85 and 0.88 Tm, nonclassical nucleation events arise. Specifically, the pathway toward an elongated nucleus becomes as important as the pathway toward a near-rounded nucleus. To explain the distinct nucleation phenomena at different supercoolings, a notion of a "transition layer" (or liquid-blob-like layer) is proposed. Here, the transition layer is to describe the interfacial region between the nucleus and aqueous solution, and this layer entails two functionalities: (1) it tends to retain CH4 depending on the degrees of supercooling and (2) it facilitates collision among CH4, which thus promote the incorporation of CH4 into nucleus. Our simulation indicates that compared to the near-rounded nucleus, the transition layer surrounding the elongated nucleus is more evident with the higher collision rate among CH4 molecules. As such, the transition layer tends to promote the elongated nucleus pathway, while offsetting the cost of larger surface free energy associated with the elongated nucleus. At 0.92 Tm, however, the transition layer gradually disappears, and classical nucleation events dominate. Overall, the notion of "transition layer" offers deeper insight into the NGH nucleation at different degrees of supercooling and could be extended to describe other types of hydrate nucleation.

Salt-Induced Coil-Globule Transition of Sulfonate-Modified HPAM is Affected by the Branched Chain Length.

Polymer flooding is a cheap and efficient method for tertiary oil recovery. However, the failure of partially hydrolyzed polyacrylamide (HPAM) molecules reduces the oil displacement efficiency under high salinity conditions. In this study, we modified HPAM molecules by sulfonic acid groups with different branched chain lengths, and we characterized the structures of these molecules in different salinity solutions through all-atoms molecular dynamics simulation. Compared with the acrylic group, the sulfonate group has excellent salt resistance because of its weak ability to attract cations. When using different lengths of branched linked branch sulfonates, increasing the length of the branched chain can improve the movement ability of sulfonates, so as to play a better salt resistance effect. However, excessive growth of branched chains can cause their association with each other and can lead to polymer folding. Therefore, we believe that the branched chain length of sulfonate should be moderately increased. These results are expected to provide theoretical support for the design and use of salt-resistant polymers..

Unraveling nucleation pathway in methane clathrate formation.

Methane clathrates are widespread on the ocean floor of the Earth. A better understanding of methane clathrate formation has important implications for natural-gas exploitation, storage, and transportation. A key step toward understanding clathrate formation is hydrate nucleation, which has been suggested to involve multiple evolution pathways. Herein, a unique nucleation/growth pathway for methane clathrate formation has been identified by analyzing the trajectories of large-scale molecular dynamics (MD) simulations. In particular, ternary water-ring aggregations (TWRAs) have been identified as fundamental structures for characterizing the nucleation pathway. Based on this nucleation pathway, the critical nucleus size and nucleation timescale can be quantitatively determined. Specifically, a methane hydration layer compression/shedding process is observed to be the critical step in (and driving) the nucleation/growth pathway, which is manifested through overlapping/compression of the surrounding hydration layers of the methane molecules, followed by detachment (shedding) of the hydration layer. As such, an effective way to control methane hydrate nucleation is to alter the hydration layer compression/shedding process during the course of nucleation.

Rational Design of Covalent Organic Frameworks as Gas Diffusion Layers for Multi-atmosphere Lithium-Air Batteries.

Non-aqueous Li-air batteries, despite their high energy density and low cost, have not been deployed practically due to their instability in ambient air, where moisture causes parasitic reactions and shortens their life drastically. Here, we demonstrate the rational design of nanoporous covalent organic frameworks (COFs) as effective gas diffusion layers (GDLs) to address this constraint. The COF GDLs, with a tailor-made pore size of ≈1.4 nm and superhydrophobicity, can limit the intrusion of organic electrolytes and moisture into the gas diffusion channels, enabling high capacity, fast kinetics, and excellent stability of the Li-air batteries. Moreover, we achieve multi-atmosphere Li-air batteries, which can stably cycle under open ambient air (relative humidity up to 95 %) and even in various atmospheres with looping oxygen, humid air, and carbon dioxide. The design principles of our COF GDLs can be universally applied in energy storage and electrochemical systems using organic electrolytes.

Stable Two-dimensional Nanoconfined Ionic Liquids with Highly Efficient Ionic Conductivity.

Amid the burgeoning environmental concerns, electrochemical energy storage is of great demand, inspiring the rapid development of electrolytes. Quasi-liquid solid electrolytes (QLSEs) demonstrate exciting properties that combine high ionic conductivity and safety. Herein, a QLSE system is constructed by confining ionic liquids (ILs) into 2D materials-based membranes, which creates a subtle platform for the investigation of the nanoconfined ion transport process. The highest ionic conductivity increment of 506% can be observed when ILs are under nanoconfinement. Correlation of experimental results and simulation evidently prove the diffusion behaviors of ILs are remarkably accelerated when confined in nanochannels, ascribing from the promoted dissociation of ILs. Concurrently, nanoconfined ILs demonstrate a highly ordered distribution, lower interplay, and higher free volume compared against bulk systems. This work reveals and analyzes the phenomenon of ionic conductivity elevation in nanoconfined ILs, and offers inspiring opportunities to fabricate the highly stable and efficient QLSEs based on layered nanomaterials for energy storage applications.

Self-assembly of an in silico designed dipeptide derivative to obtain photo-responsive vesicles.

Vesicle structures assembled from short peptides are excellent carriers for drug delivery. Modifying peptides with photo-responsive azobenzene (azo) moieties is expected to generate smart vesicles that could release cargos under stimulation of ultraviolet (UV) or visible (vis) light irradiation. The modified azo groups could dramatically affect delicate intermolecular interactions, thereby perturbing the self-assembly pathways of peptides. However, through well molecular design and screening, it should be possible to manipulate the self-assembly to obtain such smart vesicle structures. Coarse-grained (CG) molecular dynamics (MD) simulations were employed to complete the screening of azo-containing peptide derivatives and to clarify molecular mechanisms underlying the self-assembly of vesicles and the photo-response performance. Our simulations demonstrate that grafting an azo moiety to the side chain of phenylalanyl-alanine (FA) generates the F(azo)A molecule that can self-assemble into vesicles, and the addition of diphenylalanine (FF) improves the self-assembly efficiency. The formation of vesicles undergoes three stages: nucleation, fusion, and curling. On the one hand, FF molecules promote the fusion and curling stages, facilitating the co-assembly process. On the other hand, the trans-cis isomerization of F(azo)A side chains perturbs the packing of F(azo)A-FF membranes, inducing photo-responsive morphology transition and permeability change. These results are expected to promote the future regulation of self-assembly behaviors and design of smart self-assembly materials.

Molecular insight into CO2/N2 separation using a 2D-COF supported ionic liquid membrane.

The covalent organic framework (COF) shows great potential for use in gas separation because of its uniform and high-density sub-nanometer sized pores. However, most of the COF pore sizes are large, and there are mismatches with the gas pairs (3-6 Å), and the steric hindrance cannot work in gas selectivity. In this work, one type of COF (NUS-2) supported ionic liquid membrane (COF-SILM) was prepared for use in CO2/N2 separation. The separation performance was investigated using molecular dynamics simulation. There was an ultrahigh CO2 permeability up to 2.317 × 106 GPU, and a better CO2 selectivity was obtained when compared to that of N2. The physical mechanism of ultrahigh permeability and CO2 selectivity are discussed in detail. The ultrathin membrane, high-density pores and high transmembrane driving force are responsible for the ultrahigh permeability of CO2. The different adsorption capabilities of ionic liquid (IL) for CO2 and N2, as well as a gating effect, which allows CO2 passage and inhibits N2 passage, contribute to the better CO2 selectivity over N2. Moreover, the effects of the COF layer number and IL thickness on gas separation performance are also discussed. This work provides a molecular level understanding of the gas separation mechanism of COF-SILM, and the simulation results show one potential outstanding CO2 separation membrane for future applications.

Photothermal-Responsive Microporous Nanosheets Confined Ionic Liquid for Efficient CO2 Separation.

2D materials hold promising potential for novel gas separation. However, a lack of in-plane pores and the randomly stacked interplane channels of these membranes still hinder their separation performance. In this work, ferrocene based-MOFs (Zr-Fc MOF) nanosheets, which contain abundant of in-plane micropores, are synthesized as porous supports to fabricate Zr-Fc MOF supported ionic liquid membrane (Zr-Fc-SILM) for highly efficient CO2 separation. The micropores of Zr-Fc MOF nanosheets not only provide extra paths for CO2 transportation, and thus increase its permeance up to 145.15 GPU, but also endow the Zr-Fc-SILM with high selectivity (216.9) of CO2 /N2 through the nanoconfinement effect, which is almost ten times higher than common porous polymer SILM. Furthermore, based on the photothermal-responsive properties of Zr-Fc MOF, the performance is further enhanced (35%) by light irradiation through a photothermal heating process. This provides a brand new way to design light facilitating gas separation membranes.

Facilitate Gas Transport through Metal-Organic Polyhedra Constructed Porous Liquid Membrane.

Type II porous liquids are demonstrated to be promise porous materials. However, the category of porous hosts is very limited. Here, a porous host metal-organic polyhedra (MOP-18) is reported to construct type II porous liquids. MOP-18 is dissolved into 15-crown-5 as an individual cage (5 nm). Both the molecular dynamics simulations and experimental gravimetric CO2 solubility test indicate that the inner cavity of MOP-18 in porous liquids is unoccupied by 15-crown-5 and is accessible to CO2 . Thus, the prepared porous liquids show enhanced gas solubility. Furthermore, the prepared porous liquid is encapsulated into graphene oxide (GO) nanoslits to form a GO-supported porous liquid membrane (GO-SPLM). Owing to the empty cavity of MOP-18 unit cages in porous liquids that reduces the gas diffusion barrier, GO-SPLM significantly enhances the permeability of gas.

Precise Mesoscopic Model Providing Insights into Polymerization-Induced Self-Assembly.

Self-assembly of copolymer is an important approach to obtain multifarious nanostructures. Polymerization-induced self-assembly (PISA) is a recently developed and powerful copolymer self-assembly strategy. However, some researchers have reported a different morphology prepared by PISA and the traditional copolymer self-assembly using the same copolymer system. In this work, to explore the mystery, we develop a precise mesoscopic dissipative particle dynamics (DPD) model to reveal insights into the PISA of poly(4-vinylpyridine)-b-polystyrene (P4VP-b-PS). It is observed that P4VP-b-PS nanotubes can be obtained via TSA rather than PISA, which is consistent with reported experimental results. By carefully investigating the dynamics of PISA under specific solvent and monomer conditions and different polymerization rates, we propose that combining excessive monomers with multistep PISA can help to enhance the morphological regulation ability of PISA and retain a high solid content simultaneously. The findings in this study not only provide a precise modeling method for investigating copolymer self-assembly but also serve as a rational guide for future studies toward optimization of the PISA strategy.

Water desalination of a new three-dimensional covalent organic framework: a molecular dynamics simulation study.

Preparing a nanoporous membrane with high density and ordered pore sizes which allows high water permeability and salt rejection rate is the key to realize highly efficient desalination. However, preparing a nanoporous membrane with high density and order pore sizes is still extremely hard due to the limitation of experimental techniques. Recently, a 3D covalent organic framework (3D-COF) material named as the 3D-OH-COF with good crystallinity and large specific surface areas has been synthesized. Based on the structural features of the 3D-OH-COF, we speculate that it may be a good candidate for the desalination application derived from its high-density sub-nanometer pore. In this work, using molecular dynamics simulations, the possibility of the 3D-OH-COF for desalination application was explored, the influence of membrane thickness on its desalination performance was also studied, and the detailed structure and dynamics of ions and water transport in the channel of the 3D-OH-COF was discussed. The results show that the rectangular channel structure and charged H atoms are responsible for the excellent salt rejection rate (100%) and high water flux (41.44 Lit cm-2 day-1 MPa-1), respectively. Furthermore, the water flux is three orders of magnitude higher than that of the commercial reverse osmosis membrane and is four times higher than that of the theoretically reported monolayer nanoporous MoS2 membrane. It is also about 28% higher than that of the recently reported 2D-CAP membrane. This work theoretically confirms that the 3D-OH-COF is a promising membrane material for desalination applications and the underlying molecular mechanisms are clarified.

Two-dimensional hydrogen hydrates: structure and stability.

The structure and stability of two-dimensional hydrogen hydrate were investigated in this work using density functional theory. The results are in line with expectations that the occupied cages are more stable after their confinement between two parallel hydrophobic sheets. The four two-dimensional hydrogen hydrate crystals - BLHH-I, BLHH-II, BLHH-III and BLHH-IV - that we predicted were much more stable in a restricted environment than in a free environment, even close to or exceeding conventional hydrogen hydrates. Besides, we found that the stability of two-dimensional hydrates is inversely related to the increase in temperature. Our work highlights that two-dimensional hydrates provide a new research idea in the field of hydrogen storage.

CO2 -Philic Separation Membrane: Deep Eutectic Solvent Filled Graphene Oxide Nanoslits.

CO2 capture and sequestration is an energy-intensive industry to deal with the global greenhouse effect. Membrane separation is considered a cost-effective method to mitigate the emission of CO2 . Though good separation performance and stability have been reported, supported ionic liquid membranes are still not widely applied for CO2 separation due to the high cost. As a novel analogous solvent to ionic liquid, deep eutectic solvent retains the excellent merits of ionic liquid and is cheap with facile preparation. Herein, a highly CO2 -philic separation membrane is constructed by nanoconfining choline chloride/ethylene glycol (ChCl/EG) deep eutectic solvent into graphene oxide nanoslits. Molecular dynamic simulation results indicate that the confinement makes a difference to the structure of the nanoconfined ChCl/EG liquid from their bulk, which remarkably facilitates CO2 transport. By tuning the molar ratio of ChCl/EG and thickness of the membrane, the resultant membrane exhibits outstanding separation performance for CO2 with excellent selectivity over other light gases, good long-term durability, and thermal stability. This makes it a promising membrane for selective CO2 separation.

Effect of Aggregation and Adsorption Behavior on the Flow Resistance of Surfactant Fluid on Smooth and Rough Surfaces: A Many-Body Dissipative Particle Dynamics Study.

To study the effect of surfactant on the resistance of wall-bound flow, the adsorption and aggregation behaviors of surfactant fluid on both smooth and groove-patterned rough surface are investigated through many-body dissipative particle dynamics (MDPD) simulation. The MDPD models of surfactants were carefully parametrized and have been validated to be able to simulate the aggregation and adsorption behavior of surfactants. The simulation results show that the surfactant in laminar flow can only increase the flow resistance on the smooth surface. On the rough surface, surfactant with strong adsorption performance on the channel wall shows a drag reduction effect at moderate concentration. The surfactant with weak adsorption properties can enhance the flow resistance, which is even more significant than that of those surfactants with no adsorption capacity. Although heating (high temperature) can generally reduce the viscosity and flow resistance of surfactant fluid, it would cause a poor drag reduction efficiency. It may arise from the destruction of the adsorption layer and the interruption of the fluid/boundary interface. Surfactant adsorption can tune the roughness of the fluid boundary on either the smooth or rough surface in a different manner, which turns out to be highly correlated to the change in flow resistance. Compared with the adsorption layer, surfactant in the bulk fluid makes a greater contribution to enhancing the flow resistance as the concentration rises. This study is expected to be helpful in guiding the application of surfactants on the micro- and nanoscale such as lab-on-a-chip nanodevices and EOR in a low-permeability porous medium.

Composite Nanotube Ring Structures Formed by Two-Step Self-Assembly for Drug Loading/Release.

Nanotube rings are barely reported novel structures formed by the self-assembly of soft matter, as compared with nanotube structures and ring structures. The two-step self-assembly of amphiphilic copolymer AB and solvophobic copolymer CDC was studied. We found that nanotube rings can be formed from a certain mass ratio of copolymer CDC to copolymer AB and block D of certain rigidity. More interestingly, we discovered a new strategy for drug loading and release, which is different from the usual strategies reported in the literature. The present study provides a new rationale for the self-assembly of copolymers.

Optimal aggregation number of reverse micelles in supercritical carbon dioxide: a theoretical perspective.

The aggregation number is one of the most fundamental and important structural parameters for the micelle or reverse micelle (RM) system. In this work, a simple, reliable method for the determination of the aggregation number of RMs in supercritical CO2 (scCO2) was presented through a molecular dynamics simulation. The process of pulling surfactants out of the RMs one by one was performed to calculate the aggregation number. The free energies of RMs with different numbers of surfactants were calculated through this process. We found an RM with the lowest free energy, which was considered to have the optimal number of surfactants. Therefore, the optimal aggregation number of RMs was acquired. In order to explain the existence of an optimal aggregation number, detailed analyses of surfactant accumulation were conducted by combining molecular dynamics with quantum chemistry methods. The results indicated that in the RMs with the lowest free energy, the head-group and tail-terminal of the surfactants accumulated on an equipotential surface. In this case, the surfactant film could effectively separate water and CO2; thus, the lowest free energy was expected. This method determined the aggregation number of RMs by theoretical calculations that did not depend on experimental measurements. This presented approach facilitates the evaluation of the characteristics of RMs in scCO2 and can be further applied in the RM system of organic solvents or even in the micellar system.

Alternating electric field-induced ion current rectification and electroosmotic pump in ultranarrow charged carbon nanocones.

Pumping fluid in ultranarrow (sub-2 nm) synthetic channels, analogous to protein channels, has widespread applications in nanofluidic devices, molecular separation, and related fields. In this work, molecular dynamics simulations were performed to study a symmetrical sinusoidal electric field-induced electroosmotic pump in ultranarrow charged carbon nanocone (CNC) channels. The results show that the CNC channels could rectify the ion current because of the different ion flow rates in the positive and negative half circles of the sinusoidal electric field. Electroosmotic flow (EOF) rectification yielded by the ion current rectification is also revealed, and net water flow from the base to the tip of the CNC channels is observed. The simulations also show that the preferential ion current conduction direction in the ultranarrow CNC channels (from base to tip) is opposite to that in conical nanochannels with tip diameters larger than 5 nm (from tip to base). However, the preferential EOF direction is the same as that of large conical nanochannels (from base to tip). We also investigated the influences of ion concentration and the amplitudes and periods of the sinusoidal electric field on the EOF pump. The results show that high ion concentration, large amplitudes, and long periods are desired for high EOF pumping efficiency. Finally, through comparison with a constant electric field and a pressure-induced water pump, we prove that the EOF pump under an alternating electric field has a higher pump efficiency. The approach outlined in this work provides a general scheme for pumping fluid in ultranarrow charged conical nanochannels.

One-pot production of porous assemblies by PISA of star architecture copolymers: a simulation study.

The polymerization-induced self-assembly (PISA) process of star architecture copolymers is studied by dissipative particle dynamics and a reaction model. According to the simulation results, the porous vesicles can be produced directly by PISA of these copolymers. Average pore size and distribution of pore size can be influenced by αAS (the solubility between solvophilic blocks and solvent) and αAB (the solubility between solvophilic blocks and solvophobic blocks), while different self-assembly progress can be observed at different αAS and αAB. In addition, the star architecture can promote the formation of porous vesicles compared with linear copolymers. The steric effect of two solvophobic chains is verified as the key factor in formation of the porous vesicles. Further enhancement of such an effect can widen the range of αAS for production of porous vesicles, accompanied by a shrinkage of the range of αAB and a large reduction of pore size distribution. This work provides deeper understanding of the PISA of star architecture copolymers and is instructive in the experimental production of porous nano-materials.

The molecular mechanism of the inhibition effects of PVCaps on the growth of sI hydrate: an unstable adsorption mechanism.

The inhibition properties of kinetic hydrate inhibitor (KHI) molecules on the dynamic growth of a hydrate/water interface are investigated by using molecular dynamics simulations. The shape of the hydrate interface is transformed from laminar to funnel by PVCaps. Results indicate that the inhibition effects not only depend on the adsorption capacity which was believed to determine inhibition, but also on the fact that PVCaps must have some non-binding-hydrate sites that don't tend to combine with hydrate. By observing the time evolution of the distance between each component of PVCaps and hydrate, the heterocyclic ring of PVCaps mainly contributes to adsorption and can preferentially adjust itself to come into contact with a hydrate semi-large-cage. The distance between the amide of PVCaps and hydrate is about 4 Å and exceeds the range of a general hydrogen bond (3.5 Å), which proves that the non-binding-hydrate sites of PVCaps exist. On the other hand, the amide of PVCaps is at the intersection of the solid-liquid interface but has no adsorption affinity for hydrate, so this adsorption pattern indicates that the PVCaps at the hydrate interface are not stable. Due to this unstable adsorption, a repeated hydrate destruction phenomenon was revealed by the identification algorithm of hydrate and the calculation of the local number density of methane. The statistical evolution of water rings further proved the existence of non-binding-hydrate sites in PVCaps and the inhibition mechanism to destroy the hydrate cages by PVCaps. This unstable adsorption mechanism may shed light on the development of novel efficient KHIs.

Shape transition of water-in-CO2 reverse micelles controlled by the surfactant midpiece.

Designing CO2-philic surfactants for generating wormlike reverse micelles (RMs) is an effective approach to enhance the viscosity of supercritical CO2 (scCO2), however this remains challenging. Modifying the middle piece (midpiece) of surfactant tails is a potential method to generate wormlike RMs, but the underlying mechanism is still unclear. Herein, by adopting molecular dynamics simulations, the self-assembly of the hybrid surfactant FC6-HC5 in scCO2 was investigated. It was found that the FC6-HC5 with an alkyl midpiece could form spherical RMs. By introducing phenyl on the surfactant midpiece, a transformation of the RMs from a spherical shape to a wormlike shape was achieved. The improved fusion free energy was demonstrated to promote the fusion of the spherical RMs to form wormlike RMs. Further analysis indicated that, originating from the π-π interaction, the introduced phenyl assists the parallel arrangement of FC6-HC5, resulting in the improved fusion ability. Moreover, according to the analysis on interfacial properties, introducing phenyl had little effect on the surfactant CO2-philicity. Therefore, modifying the midpiece is a great method for designing hybrid surfactants to generate wormlike RMs while maintaining their high CO2-philicity. This strategy of generating wormlike RMs is expected to facilitate the application of scCO2 meeting industrial requirements.