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..

Bioinspired design of Na-ion conduction channels in covalent organic frameworks for quasi-solid-state sodium batteries.

Solid polymer electrolytes are considered among the most promising candidates for developing practical solid-state sodium batteries. However, moderate ionic conductivity and narrow electrochemical windows hinder their further application. Herein, inspired by the Na+/K+ conduction in biological membranes, we report a (-COO-)-modified covalent organic framework (COF) as a Na-ion quasi-solid-state electrolyte with sub-nanometre-sized Na+ transport zones (6.7-11.6 Å) created by adjacent -COO- groups and COF inwalls. The quasi-solid-state electrolyte enables selective Na+ transport along specific areas that are electronegative with sub-nanometre dimensions, resulting in a Na+ conductivity of 1.30×10-4 S cm-1 and oxidative stability of up to 5.32 V (versus Na+/Na) at 25 ± 1 °C. Testing the quasi-solid-state electrolyte in Na||Na3V2(PO4)3 coin cell configuration demonstrates fast reaction dynamics, low polarization voltages, and a stable cycling performance over 1000 cycles at 60 mA g-1 and 25 ± 1 °C with a 0.0048% capacity decay per cycle and a final discharge capacity of 83.5 mAh g-1.

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.

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.

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.

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.

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.

Why synthetic virus-like nanoparticles can achieve higher cellular uptake efficiency?

Experimental studies in recent years have demonstrated that the cellular uptake properties of nanoparticles can be improved by mimicking the spiky surfaces of viruses; however, little is known on how the surface topological structure of nanoparticles affects their translocation across the cell membrane. Here, by employing dissipative particle dynamics simulations, the interactions between virus-like nanoparticles (VLPs) and the lipid bilayer are investigated. The analysis of critical force for penetration demonstrates that VLPs with relatively longer and sparser spikes have better penetrability. The internalization pathway of VLPs illustrates that the spikes of VLPs can perturb the bilayer structure after VLPs adhere onto the bilayer. Furthermore, by comparing the translocation process of VLPs and spherical nanoparticles, it is found that the presence of spikes can help to increase the lateral defects in the bilayer, decrease the vertical deformation of the bilayer, and lower the density of nearby lipids during the translocation process. These effects of spikes jointly contribute to the superior penetrability of VLPs. It is expected that these findings not only enrich our understanding of how the surface topological structure affects the cellular uptake, but also pave the way for further development of VLPs for versatile biomedical applications.

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.

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.

A solution-processable and ultra-permeable conjugated microporous thermoset for selective hydrogen separation.

The synthesis of a polymer that combines the processability of plastics with the extreme rigidity of cross-linked organic networks is highly attractive for molecular sieving applications. However, cross-linked networks are typically insoluble or infusible, preventing them from being processed as plastics. Here, we report a solution-processable conjugated microporous thermoset with permanent pores of ~0.4 nm, prepared by a simple heating process. When employed as a two-dimensional molecular sieving membrane for hydrogen separation, the membrane exhibits ultrahigh permeability with good selectivity for H2 over CO2, O2, N2, CH4, C3H6 and C3H8. The combined processability, structural rigidity and easy feasibility make this polymeric membrane promising for large-scale hydrogen separations of commercial and environmental relevance.

Manipulating Hybrid Nanostructures by the Cooperative Assembly of Amphiphilic Oligomers and Triblock Janus Nanoparticles.

The cooperative assembly of nanoparticles and amphiphilic molecules has emerged as an appealing strategy for fabricating hybrid nanomaterials for a wide range of potential applications. However, it is challenging to precisely manipulate hybrid nanostructures. In this study, extensive dissipative particle dynamics simulations are carried out to investigate the cooperative assembly of amphiphilic oligomers and triblock Janus nanoparticles with different hydrophobic-hydrophilic patches. Three different hybrid nanostructures (networks, disks, and vesicles) are observed from the simulations. The structural characteristics and kinetic pathways are analyzed in detail. We reveal that the hydrophobic-hydrophilic patches in the triblock Janus nanoparticles significantly affect the arrangement of amphiphiles and nanoparticles, as well as the orientational degree of freedom between nanoparticles; therefore, the triblock Janus nanoparticles can function as a robust structure-directing agent to regulate the spatial organization of nanoparticles in networks, the curvature of disks, and the size of vesicles. This study demonstrates the cooperative assembly can serve as an efficient platform for the engineering of hybrid nanomaterials with tailored nanostructures.

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.

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.

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.

Temperature controlled diffusion of hydroxide ions in 1D channels of Ni-MOF-74 for its complete conformal hydrolysis to hierarchical Ni(OH)2 supercapacitor electrodes.

Conformal hydrolysis of MOF precursors is a promising strategy to prepare hierarchical metal hydroxide electrode materials on a large scale with low cost and high efficiency. However, a complete transformation is challenging due to the normal "outside-in" conversion process. After studying the hydrolysis of Ni-MOF-74, which has regular 1D channels, we suggest that the transformation to Ni(OH)2 can occur simultaneously outside and within the precursor depending on the treatment temperature. Molecular dynamics simulations reveal that a higher temperature weakens the steric effects of OH- ions and facilitates the diffusion in the regular channels, and therefore, a complete transformation from Ni-MOF-74 to Ni(OH)2 is achieved. It is for the first time demonstrated that the 1D channels of MOFs are utilized for the complete conformal hydrolysis of Ni-MOF-74 to Ni(OH)2 electrode materials. Meanwhile, we also perform pioneering work illustrating that the complete conformal hydrolysis is the key to the improved supercapacitor performances of the MOF-derived Ni(OH)2 electrodes. The prepared Ni(OH)2 electrode under the optimized conditions has a specific capacity of 713.2 C g-1 at a current density of 1 A g-1, which is at least 28% larger than those of the Ni(OH)2 prepared at other temperatures. The detailed analyses based on CV and EIS of the obtained Ni(OH)2 electrodes indicate that the residual MOFs within electrodes due to incomplete hydrolysis significantly influence the diffusion length and diffusion efficiency of OH-, drastically lowering the supercapacitor performances.

Cooperative assembly of Janus particles and amphiphilic oligomers: the role of Janus balance.

Cooperative assembly of nanoparticles and amphiphiles has emerged as a significant strategy for constructing hybrid nanocomposites with desired architectures and properties. It is of great significance to develop novel hybrid nanostructures with controlled spatial localization of nanoparticles within hybrid assemblies. Here, by adopting dissipative particle dynamics simulations, the cooperative assembly of Janus particles and amphiphilic oligomers is studied. We demonstrate that a variety of defined hybrid nanostructures such as balls, sticks, disks, lines, vesicles, and networks can be achieved by the cooperative assembly of Janus particles and amphiphilic oligomers. Furthermore, the investigation of the kinetic pathway illustrates that the formation of hybrid assemblies is an entropy-driven process. Our simulation results suggest that the Janus balance of nanoparticles can significantly affect the structure and size of hybrid aggregates and the spatial localization of Janus particles within hybrid assemblies. These findings not only enrich our understanding of the cooperative assembly of Janus nanoparticles and amphiphiles, but also offer a feasible strategy to prepare hybrid materials with controlled localization of nanoparticles.