Chemical looping combustion (CLC) is a promising and novel technology for carbon dioxide (CO2) capture with a relatively low energy consumption and cost. CuO, one of the most attractive oxygen carriers (OCs) for carbon dioxide (CO) oxidation, suffers from sintering and agglomeration during the reduction process. Applying an electric field (EF) may promote the CO oxidation process on the CuO surface, which could mitigate sintering and agglomeration by decreasing operating temperatures with negligible combustion efficiency loss. This study performs density functional theory (DFT) simulations to investigate the effects of EF on the oxidation of CO on the CuO (111) surface. The results indicate that both the orientation and strength of the EF can significantly affect the oxidation characteristics of CO on the CuO (111) surface such as total reaction energy, energy barriers of reactions, CO adsorption, and CO2 desorption. For the first time, this study reveals the role of EF in enhancing CO oxidation through CLC processes via first-principle calculations. Such findings could provide new strategies to improve the performance of CLC processes.
Carbon dioxide (CO2) electroreduction by metal-nitrogen-doped carbon (MNC) catalysts is a promising and efficient method to mitigate global warming by converting CO2 molecules to value-added chemicals. In this research, we systematically studied the behaviours of single and dual-atom Cu catalysts during the CO2 electroreduction process using density functional theory (DFT) calculations. Two structures, i.e., CuNC-4-pyridine and CuCuNC-4a, were found to be beneficial for C2 chemical generation with relatively high stabilities. Subsequently, we explored the detailed pathways of key products (CO, HCOOH, CH3OH, CH4, C2H6O, C2H4 and C2H6) during CO2 electroreduction on CuNC-4-pyridine and CuCuNC-4a. This research reveals the mechanisms of key product formation during CO2 electroreduction on CuNC-4-pyridine and CuCuNC-4a, which would provide important insights to guide the design of MNC catalysts with low limiting potentials and high product selectivity.
Flame spray pyrolysis (FSP) provides an advantageous synthetic route for LiNi1-x-yCoxMnyO2 (NCM) materials, which are one of the most practical and promising cathode materials for Li-ion batteries. However, a detailed understanding of the NCM nanoparticle formation mechanisms through FSP is lacking. To shed light on the evaporation of NCM precursor droplets in FSP, in this work, we employ classical molecular dynamics (MD) simulations to explore the dynamic evaporation process of nanodroplets composed of metal nitrates (including LiNO3, Ni(NO3)2, Co(NO3)2, and Mn(NO3)2 as solutes) and water (as solvent) from a microscopic point of view. Quantitative analysis on the evaporation process has been performed by tracking the temporal evolution of key features including the radial distribution of mass density, the radial distribution of number density of metal ions, droplet diameter, and coordination number (CN) of metal ions with oxygen atoms. Our MD simulation results show that during the evaporation of an MNO3-containing (M = Li, Ni, Co, or Mn) nanodroplet, Ni2+, Co2+, and Mn2+ will precipitate on the droplet surface, forming a solvent-core-solute-shell structure; whereas the distribution of Li+ within the evaporating LiNO3-containing droplet is more even due to the high diffusivity of Li+ compared with other metal ions. For the evaporation of a Ni(NO3)2- or Co(NO3)2-containing nanodroplet, the temporal evolution of the CN of M-OW (M = Ni or Co; OW represents O atoms from water) suggests a "free H2O" evaporation stage, during which both CN of M-OW and CN of M-ON are unchanged with time. Evaporation rate constants at various conditions are extracted by making analogy to the classical D2 law for droplet evaporation. Unlike Ni or Co, CN of Mn-OW keeps changing with time, yet the temporal evolution of the squared droplet diameter indicates the evaporation rate for a Ni(NO3)2-, Co(NO3)2-, or Mn(NO3)2-containing droplet is hardly affected by the different types of the metal ions.
Ab initio molecular dynamics (AIMD) is an established method for revealing the reactive dynamics of complex systems. However, the high computational cost of AIMD restricts the explorable length and time scales. Here, we develop a fundamentally different approach using molecular dynamics simulations powered by a neural network potential to investigate complex reaction networks. This potential is trained via a workflow combining AIMD and interactive molecular dynamics in virtual reality to accelerate the sampling of rare reactive processes. A panoramic visualization of the complex reaction networks for decomposition of a novel high explosive (ICM-102) is achieved without any predefined reaction coordinates. The study leads to the discovery of new pathways that would be difficult to uncover if established methods were employed. These results highlight the power of neural network-based molecular dynamics simulations in exploring complex reaction mechanisms under extreme conditions at the ab initio level, pushing the limit of theoretical and computational chemistry toward the realism and fidelity of experiments.
Molecular Dynamics Simulation , Neural Networks, Computer
As a powerful mesoscale approach, the lattice Boltzmann method (LBM) has been widely used for the numerical study of complex multiphase flows. Recently, Luo et al. [Philos. Trans. R. Soc. A: Math. Phys. Eng. Sci. 379, 20200397 (2021)10.1098/rsta.2020.0397] proposed a unified lattice Boltzmann method (ULBM) to integrate the widely used lattice Boltzmann collision operators into a unified framework. In this study, we incorporate additional features into this ULBM in order to simulate multiphase flow under realistic conditions. A nonorthogonal moment set [Fei et al., Phys. Rev. E 97, 053309 (2018)10.1103/PhysRevE.97.053309] and the entropic-multi-relaxation-time (KBC) lattice Boltzmann model are used to construct the collision operator. An extended combined pseudopotential model is proposed to realize multiphase flow simulation at high-density ratio with tunable surface tension over a wide range. The numerical results indicate that the improved ULBM can significantly decrease the spurious velocities and adjust the surface tension without appreciably changing the density ratio. The ULBM is validated through reproducing various droplet dynamics experiments, such as binary droplet collision and droplet impingement on superhydrophobic surfaces. Finally, the extended ULBM is applied to complex droplet dynamics, including droplet pancake bouncing and droplet splashing. The maximum Weber number and Reynolds number in the simulation reach 800 and 7200, respectively, at a density ratio of 1000. The study demonstrates the generality and versatility of ULBM for incorporating schemes to tackle challenging multiphase problems.
We present a molecular dynamics simulation study on the effects of sodium chloride addition on stability of a nitrogen bulk nanobubble in water. We find that the lifetime of the bulk nanobubble is extended in the presence of NaCl and reveal the underlying mechanisms. We do not observe spontaneous accumulation or specific arrangement of ions/charges around the nanobubble. Importantly, we quantitatively show that the N2 molecule selectively diffuses through water molecules rather than pass by any ions after it leaves the nanobubble due to the much weaker water-water interactions than ion-water interactions. The strong ion-water interactions cause hydration effects and disrupt hydrogen bond networks in water, which leave fewer favorable paths for the diffusion of N2 molecules, and by that reduce the degree of freedom in the dissolution of the nanobubble and prolong its lifetime. These results demonstrate that the hydration of ions plays an important role in stability of the bulk nanobubble by affecting the dynamics of hydrogen bonds and the diffusion properties of the system, which further confirm and interpret the selective diffusion path of N2 molecules and the extension of lifetime of the nanobubble. The new atomistic insights obtained from the present research could potentially benefit the practical application of bulk nanobubbles.
Modeling liquid-vapor phase change using the lattice Boltzmann (LB) method has attracted significant attention in recent years. In this paper, we propose an improved three-dimensional thermal multiphase LB model for simulating liquid-vapor phase change. The proposed model has the following features. First, it is still within the framework of the thermal LB method using a temperature distribution function and therefore retains the fundamental advantages of the thermal LB method. Second, in the existing thermal LB models for liquid-vapor phase change, the finite-difference computations of the gradient terms ∇·u and ∇T usually require special treatment at boundary nodes, while in the proposed thermal LB model these two terms are calculated locally. Moreover, in some of the existing thermal LB models, the error term ∂_{t_{0}}(Tu) is eliminated by adding local correction terms to the collision process in the moment space, which causes these thermal LB models to be limited to the D2Q9 lattice in two dimensions and the D3Q15 or D3Q19 lattice in three dimensions. Conversely, the proposed model does not suffer from such an error term and therefore the thermal LB equation can be constructed on the D3Q7 lattice, which simplifies the model and improves the computational efficiency. Numerical simulations are carried out to validate the accuracy and efficiency of the proposed thermal multiphase LB model for simulating liquid-vapor phase change.
The classical D^{2}-Law states that the square of the droplet diameter decreases linearly with time during its evaporation process, i.e., D^{2}(t)=D_{0}^{2}-Kt, where D_{0} is the droplet initial diameter and K is the evaporation constant. Though the law has been widely verified by experiments, considerable deviations are observed in many cases. In this work, a revised theoretical analysis of the single droplet evaporation in finite-size open systems is presented for both two-dimensional (2D) and 3D cases. Our analysis shows that the classical D^{2}-Law is only applicable for 3D large systems (Lâ«D_{0}, L is the system size), while significant deviations occur for small (L≤5D_{0}) and/or 2D systems. Theoretical solution for the temperature field is also derived. Moreover, we discuss in detail the proper numerical implementation of droplet evaporation in finite-size open systems by the mesoscopic lattice Boltzmann method (LBM). Taking into consideration shrinkage effects and an adaptive pressure boundary condition, droplet evaporation in finite-size 2D/3D systems with density ratio up to 328 within a wide parameter range (K=[0.003,0.18] in lattice units) is simulated, and remarkable agreement with the theoretical solution is achieved, in contrast to previous simulations. The present work provides insights into realistic droplet evaporation phenomena and their numerical modeling using diffuse-interface methods.
The effect of rotation on small-scale characteristics and scaling law in the mixing zone of the three-dimensional turbulent Rayleigh-Taylor instability (RTI) is investigated by the lattice Boltzmann method at small Atwood number. The mixing zone width h(t), the root mean square of small scale fluctuation, the spectra, and the structure functions are obtained to analyze the rotating effect. We mainly focus on the process of the development of plumes and discuss the physical mechanism in the mixing zone in rotating and nonrotating systems. The variation of kinetic energy spectra E_{u} and temperature energy spectra E_{θ} with the dimensionless rotation Ωτ demonstrate the suppression effect of rotation. Two scaling laws between the mixing layer width h(t) and dimensionless time t/τ are obtained at various Coriolis forces(sqrt[h(t)]≃t^{0.9} and sqrt[h(t)]≃t^{0.35}). The rotation increasingly suppresses the growth of the mixing layer width h(t). The velocity and temperature fluctuations are also suppressed by the rotation effect. The relation between the Nusselt number (Nu) and the Rayleigh number (Ra) indicates that the heat transfer is suppressed by the rotation effect in the rotating RT system. The width of the inertial subrange increasingly narrows with increasing Ωτ.
Endothelial glycocalyx (EG) is a forest-like structure, covering the lumen side of blood vessel walls. EG is exposed to the mechanical forces of blood flow, mainly shear, and closely associated with vascular regulation, health, diseases, and therapies. One hallmark function of the EG is mechanotransduction, which means the EG senses the mechanical signals from the blood flow and then transmits the signals into the cells. Using numerical modelling methods or in silico experiments to investigate EG-related topics has gained increasing momentum in recent years, thanks to tremendous progress in supercomputing. Numerical modelling and simulation allows certain very specific or even extreme conditions to be fulfilled, which provides new insights and complements experimental observations. This mini review examines the application of numerical methods in EG-related studies, focusing on how computer simulation contributes to the understanding of EG as a mechanotransducer. The numerical methods covered in this review include macroscopic (i.e., continuum-based), mesoscopic [e.g., lattice Boltzmann method (LBM) and dissipative particle dynamics (DPD)] and microscopic [e.g., molecular dynamics (MD) and Monte Carlo (MC) methods]. Accounting for the emerging trends in artificial intelligence and the advent of exascale computing, the future of numerical simulation for EG-related problems is also contemplated.
In this work, we develop a unified lattice Boltzmann model (ULBM) framework that can seamlessly integrate the widely used lattice Boltzmann collision operators, including the Bhatnagar-Gross-Krook or single-relation-time, multiple-relaxation-time, central-moment or cascaded lattice Boltzmann method and multiple entropic operators (KBC). Such a framework clarifies the relations among the existing collision operators and greatly facilitates model comparison and development as well as coding. Importantly, any LB model or treatment constructed for a specific collision operator could be easily adopted by other operators. We demonstrate the flexibility and power of the ULBM framework through three multiphase flow problems: the rheology of an emulsion, splashing of a droplet on a liquid film and dynamics of pool boiling. Further exploration of ULBM for a wide variety of phenomena would be both realistic and beneficial, making the LBM more accessible to non-specialists. This article is part of the theme issue 'Progress in mesoscale methods for fluid dynamics simulation'.
Vascular endothelial cells and circulating red blood cell (RBC) surfaces are both covered by a layer of bushy glycocalyx. The interplay between these glycocalyx layers is hardly measurable and insufficiently understood. This study aims to investigate and qualify the possible interactions between the glycocalyces of RBCs and endothelial cells using mathematical modeling and numerical simulation. Dissipative particle dynamics (DPD) simulations are conducted to investigate the response of the endothelial glycocalyx (EG) to varying ambient conditions. A two-compartment model including EG and flow and a three-compartment model comprising EG, RBC glycocalyx, and flow are established. The two-compartment analysis shows that a relatively fast flow is associated with a predominantly bending motion of the EG, whereas oscillatory motions are predominant in a relatively slow flow. Results show that circulating RBCs cause the contactless deformation of EG. Its deformation is dependent on the chain layout, chain length, bending stiffness, RBC-to-EG distance, and RBC velocities. Specifically, shorter EG chains or RBC-to-EG distance leads to greater relative deflections of EG. Deformation of EG is enhanced when the EG chains are rarefied or RBCs move faster. The bending stiffness maintains stretching conformation of EG. Moreover, a compact EG chain layout and shedding EG chains disturb the neighboring flow field, causing disordered flow velocity distributions. In contrast, the movement of EG chains on RBC surfaces exerts a marginal driving force on RBCs. The DPD method is used for the first time, to our knowledge, in the three-compartment system to explore the cross talk between EG and RBC glycocalyx. This study suggests that RBCs drive the EG deformation via the near-field flow, whereas marginal propulsion of RBCs by the EG is observed. These new, to our knowledge, findings provide a new angle to understand the roles of glycocalyx in mechanotransduction and microvascular permeability and their perturbations under idealized pathophysiologic conditions associated with EG degradation.
Endothelial Cells , Glycocalyx , Computer Simulation , Erythrocytes , Mechanotransduction, Cellular
A multiple-relaxation-time discrete Boltzmann model (DBM) is proposed for multicomponent mixtures, where compressible, hydrodynamic, and thermodynamic nonequilibrium effects are taken into account. It allows the specific heat ratio and the Prandtl number to be adjustable, and is suitable for both low and high speed fluid flows. From the physical side, besides being consistent with the multicomponent Navier-Stokes equations, Fick's law, and Stefan-Maxwell diffusion equation in the hydrodynamic limit, the DBM provides more kinetic information about the nonequilibrium effects. The physical capability of DBM to describe the nonequilibrium flows, beyond the Navier-Stokes representation, enables the study of the entropy production mechanism in complex flows, especially in multicomponent mixtures. Moreover, the current kinetic model is employed to investigate nonequilibrium behaviors of the compressible Kelvin-Helmholtz instability (KHI). The entropy of mixing, the mixing area, the mixing width, the kinetic and internal energies, and the maximum and minimum temperatures are investigated during the dynamic KHI process. It is found that the mixing degree and fluid flow are similar in the KHI process for cases with various thermal conductivity and initial temperature configurations, while the maximum and minimum temperatures show different trends in cases with or without initial temperature gradients. Physically, both heat conduction and temperature exert slight influences on the formation and evolution of the KHI morphological structure.
In the present research, the sodium ion transport across the endothelial glycocalyx layer (EGL) under an imposed electric field is investigated, for the first time, using a series of molecular dynamics simulations. The electric field is perpendicularly imposed on the EGL with varying strengths. The sodium ion molarity difference between the inner and outer layers of EGL, Δc, is used to quantify the sodium transport in the presence of the negatively charged glycocalyx sugar chains. Results suggest that a weak electric field increases Δc, regardless of whether the electric field is imposed perpendicularly inward or outward. By contrast, a strong electric field drives sodium ions to travel in the same orientation as the electric field. Scrutiny of the charge distribution of the glycocalyx sugar chains suggests that the electric field modifies the spatial layouts of glycocalyx atoms as it drives the transport of sodium ions. The modification in glycocalyx layouts further changes the inter-molecular interactions between glycocalyx sugar chains and sodium ions, thereby limiting the electric field control of ion transport. The sodium ions, in turn, alter the apparent bending stiffness of glycocalyx. Moreover, the negative charges of the glycocalyx sugar chains play an important role in maintaining structural stability of endothelial glycocalyx. Based on the findings, a hypothesis is proposed regarding the existence of a strength threshold of the electric field in controlling charged particles in the endothelium, which offers an alternative explanation for contrasting results in previous experimental observations.
Endothelium/metabolism , Glycocalyx/metabolism , Sodium/metabolism , Cardiovascular System/metabolism , Electricity , Humans , Ion Transport , Models, Biological , Molecular Dynamics Simulation
Contact angle hysteresis, defined as the difference between advancing and receding contact angles, is an important phenomenon in multiphase flow on a wetting surface. In this study, a modified pseudo-potential lattice Boltzmann (LB) multiphase model with tunable surface tension is proposed, which is further coupled with the geometrical formulation contact angle scheme to investigate the motion of droplets invoking the contact angle hysteresis. We focus on the dynamic behaviour of droplets driven by a body force at the Bond number ranging from 1 to 6, which is defined as the ratio of the body force to the capillary force. The droplet morphology change is examined by varying (i) the Bond number and (ii) the hysteresis window. Results show the droplet morphology evolution can be classified into different stages, including stretch, relaxation, and equilibrium. The droplet oscillation phenomenon at large Bond numbers at the equilibrium stage is observed for the first time. In addition, it is found that such oscillation can lead to the breakup and/or coalescence of droplets when the surface waves spread on the top of the droplet. Furthermore, there is slight oscillation of the normalized length, width and height at the equilibrium stage for the neutral hysteresis window while more dramatic oscillation will appear for the hydrophobic hysteresis window.
The lipid membrane of endothelial cells plays a pivotal role in maintaining normal circulatory system functions. To investigate the response of the endothelial cell membrane to changes in vascular conditions, an atomistic model of the lipid membrane interspersed with Syndecan-4 core protein was established based on experimental observations and a series of molecular dynamics simulations were undertaken. The results show that flow results in continuous deformation of the lipid membrane, and the degree of membrane deformation is not in monotonic relationship with the environmental changes (either the changes in blood velocity or the alteration of the core protein configuration). An explanation for such non-monotonic relationship is provided, which agrees with previous experimental results. The elevation of the lipid membrane surface around the core protein of the endothelial glycocalyx was also observed, which can be mainly attributed to the Coulombic interactions between the biomolecules therein. The present study demonstrates that the blood flow can deform the lipid membrane directly via the interactions between water molecules and lipid membrane atoms thereby affecting mechanosensing; it also presents an additional force transmission pathway from the flow to the lipid membrane via the glycocalyx core protein, which complements previous mechanotransduction hypothesis.
Cell Membrane/physiology , Endothelial Cells/physiology , Syndecan-4/physiology , Molecular Dynamics Simulation , Regional Blood Flow , Water/physiology
AIM: Endothelial glycocalyx (EG) plays a pivotal role in a plethora of diseases, like cardiovascular and renal diseases. One hallmark function of the EG as a mechanotransducer which transmits mechanical signals into cytoplasm has been documented for decades. However, the basic question - how the glycocalyx transmits the flow shear stress- is unanswered so far. Our aim is to shed light on the fundamental mode of signal transmission from flow to the endothelial cytoskeleton. METHODS: We conduct a series of large-scale molecular dynamics computational experiments to investigate the dynamics of glycocalyx under varying conditions (changing blood flow velocities and shedding of glycocalyx sugar chains). RESULTS: We have identified that the main pathway of signal transmission in this system manifests as a scissors-like motion of the Syndecan-4 core protein. Results have suggested that the force transmitted into the cytoskeleton with an order of 10 ~ 100 pN, and the main function of sugar chains of a glycocalyx element is to protect the core proteins from severe conformational changes thereby maintaining the functionality of the EG. CONCLUSION: This research provides a reconciling explanation for a longstanding debate about the force transmission threshold based on our findings. A new explanation has also been provided to relate the role of the EG as a mechanotransducer to its function as a microvascular barrier: the EG regulates the mechanotransduction by altering the median value and variation range of the scissor angle, and the EG governs the microvascular barrier via controlling the scissor angle which will affect the intercellular cleft.
Endothelium, Vascular/cytology , Endothelium, Vascular/metabolism , Glycocalyx/metabolism , Syndecan-4/metabolism , Blood Flow Velocity , Cytoskeleton/metabolism , Humans , Mechanotransduction, Cellular , Molecular Dynamics Simulation , Motion , Protein Multimerization , Stress, Mechanical
The rheology of pressure-driven flows of two-dimensional dense monodisperse emulsions in neutral wetting microchannels is investigated by means of mesoscopic lattice Boltzmann simulations, capable of handling large collections of droplets, in the order of several hundreds. The simulations reveal that the fluidization of the emulsion proceeds through a sequence of discrete steps, characterized by yielding events whereby layers of droplets start rolling over each other, thus leading to sudden drops of the relative effective viscosity. It is shown that such discrete fluidization is robust against loss of confinement, namely it persists also in the regime of small ratios of the droplet diameter over the microchannel width. We also develop a simple phenomenological model which predicts a linear relation between the relative effective viscosity of the emulsion and the product of the confinement parameter (global size of the device over droplet radius) and the viscosity ratio between the disperse and continuous phases. The model shows excellent agreement with the numerical simulations. The present work offers new insights to enable the design of microfluidic scaffolds for tissue engineering applications and paves the way to detailed rheological studies of soft-glassy materials in complex geometries.
The pseudopotential multiphase lattice Boltzmann (LB) model is a very popular model in the LB community for simulating multiphase flows. When the multiphase modeling involves a solid boundary, a numerical scheme is required to simulate the contact angle at the solid boundary. In this work, we aim at investigating the implementation of contact angles in the pseudopotential LB simulations with curved boundaries. In the pseudopotential LB model, the contact angle is usually realized by employing a solid-fluid interaction or specifying a constant virtual wall density. However, it is shown that the solid-fluid interaction scheme yields very large spurious currents in the simulations involving curved boundaries, while the virtual-density scheme produces an unphysical thick mass-transfer layer near the solid boundary although it gives much smaller spurious currents. We also extend the geometric-formulation scheme in the phase-field method to the pseudopotential LB model. Nevertheless, in comparison with the solid-fluid interaction scheme and the virtual-density scheme, the geometric-formulation scheme is relatively difficult to implement for curved boundaries and cannot be directly applied to three-dimensional space. By analyzing the features of these three schemes, we propose an improved virtual-density scheme to implement contact angles in the pseudopotential LB simulations with curved boundaries, which does not suffer from a thick mass-transfer layer near the solid boundary and retains the advantages of the original virtual-density scheme, i.e., simplicity, easiness for implementation, and low spurious currents.
In this paper, an improved three-dimensional color-gradient lattice Boltzmann (LB) model is proposed for simulating immiscible two-phase flows. Compared with the previous three-dimensional color-gradient LB models, which suffer from the lack of Galilean invariance and considerable numerical errors in many cases owing to the error terms in the recovered macroscopic equations, the present model eliminates the error terms and therefore improves the numerical accuracy and enhances the Galilean invariance. To validate the proposed model, numerical simulations are performed. First, the test of a moving droplet in a uniform flow field is employed to verify the Galilean invariance of the improved model. Subsequently, numerical simulations are carried out for the layered two-phase flow and three-dimensional Rayleigh-Taylor instability. It is shown that, using the improved model, the numerical accuracy can be significantly improved in comparison with the color-gradient LB model without the improvements. Finally, the capability of the improved color-gradient LB model for simulating dynamic two-phase flows at a relatively large density ratio is demonstrated via the simulation of droplet impact on a solid surface.
